Catalyst compositions and processes for olefin polymers and copolymers

ABSTRACT

The present invention is directed to certain novel late transition metal salicylaldimine chelates and, further, to novel bidentate ligand compounds of substituted salicylaldimine, and their utility as polymerization catalysts alone or in combination with adjunct agent and/or Lewis base in processes of polymerizing olefin monomers and copolymerizing olefin monomers with functionalized olefin monomers.

This application is a divisional application of copending U.S.application Ser. No. 09/007,443, filed Jan. 15, 1998, which is acontinuation-in-part application of U.S. application Ser. No.08/822,531, filed Mar. 24, 1997, now abandoned each of which isincorporated herein in its entirety by reference.

This invention was made with United States Government support underContract No. 70NANB5H1136 awarded by the Department of Commerce'sNational Institute of Standards and Technology. The United States hascertain rights in the invention.

The present invention is directed to organometallic catalysts andcatalyst compositions useful in the polymerization of alpha-olefinsalone or in combination with functionalized olefins, certain bidentateligand compounds useful in providing the subject catalysts, processes offorming the bidentate ligand compounds and catalysts therefrom,processes of forming olefin oligomers and polymers utilizing the subjectcatalysts and catalyst compositions, and the oligomers and polymersformed therefrom.

The polyolefin industry has relied on various catalyst and initiatorsystems. The polymerization of ethylene and other non-polar 1-olefinshas been commonly accomplished using organometallic Ziegler-Nattacoordination-type catalysts, chromium catalysts, other early transitionmetal catalysts, as well as free-radical type initiators. Although thearray of catalysts available provides different approaches to themanufacture of polyolefins with differing physical and mechanicalproperties, these catalysts are highly susceptible to a range ofsubstances which poison or deactivate the catalyst's activity. It iswell known that even trace amounts of oxygen, carbon monoxide, acetyleneor water cause deactivation. Further, catalyst deactivation is caused byorganic compounds having oxygen donor groups such as ethers, esters,alcohols, or ketones. Industrial application of these organometalliccatalysts requires careful and elaborate measures to assure the absenceof such poisons. Because these catalysts are easily poisoned, they tendto form low molecular weight materials, can not be used to providecopolymerization of ethylene with an oxygenated functional monomer, suchas an ester, acid or ether functionalized olefin, and generally mayproduce highly branched polymer products.

More recently, olefin polymerizaton catalysts have been developed whichare less oxophilic than the early transition metal counterparts. Forexample, U.S. Pat. Nos. 4,310,716; 4,382,153; 4,293,727; 4,301,318; and4,293,502 each disclose late transition metal (e.g. Ni) complexes whichprovide low molecular weight oligomers of ethylene. Further,polymerization of ethylene has been successfully shown using complexesbased on phosphorous ylide ligands in U.S. Pat. No. 4,537,982 as well asin U.S. Pat. Nos. 4,698,403; 4,716,205; and 4,906,754. These nickelbased catalysts formed from P—O bidentate ligands have been shown toprovide high activity in the oligomerization and polymerization ofethylene. Still more recently, L. K. Johnson et al in J. Am. Chem. Soc.1995 117, 6414, reported the formation and use of Pd(II) and Ni(II)based cationic complexes formed from diimine ligands to provide highmolecular weight polyolefins. Finally, WO 96/23010 describes a processfor the polymerization of olefins using a variety of transition metalcomplexes of certain diimine bidentate ligands. In many cases thepolymerizations provided highly branched polyolefins and were not shownto be useful in providing functionalized copolymer products. Further, inthose instances where functionalized copolymers were formed, it wasshown that the functional groups reside exclusively at the end of chainbranches.

Certain processes and cationic nickel (II) catalyst compositions havebeen described also by L. K. Johnson et al in WO 97/02298. Thesecationic complexes are described as active for the polymerization ofethylene and other olefins. They require use of an acid of anon-coordinating mono-anion, or some combination of compounds that willgenerate such acid, in order for the catalyst composition to be renderedactive towards olefin polymerization. The present neutral complexes, aswell as the use of a Lewis base is not suggested by Johnson et al.

Although Löfgren et al, in Macromolecules 1997, 30, 171-175 describepolymerization of ethylene by cationic zirconium salen bis-chloridecomplexes with or without a Lewis base (tetrahydrofuran), they show thatthe catalyst composition exhibits only low levels of activity. There aremany references describing the deleterious effect of Lewis base towardlate transition metal catalyst compositions as well as single-sitecatalyst compositions of the metallocene type. For example, EP 94/304642and EP 94/630910 disclose that Lewis base, such as dialkyl ether,substantially terminates olefin polymerization by a single-site catalystcomposition composed of a metallocene compound and partially hydrolyzedaluminum alkyl compound (aluminoxane). Additionally, U.S. Pat. No.5,571,881 and WO 95/14048 indicate that an unsaturated Lewis base, e.g.,vinyl ether, either reacts with the cationic late transition metalcatalysts to destroy their activity or causes reduction of the resultantpolymer molecular weight.

It is highly desired to provide a catalyst for the oligomerization andpolymerization of olefins, in particular ethylene, which provides asubstantially linear (low degree of branching) product. It is alsohighly desired to provide a nonionic catalyst which can provide thelinear polymer product. It is still further desired to provide anonionic catalyst which is capable of providing a product of highmolecular weight is capable of promoting copolymerization of olefin andfunctionalized olefin monomer units.

Finally, it is desired to provide a catalyst composition composed of anon-ionic catalyst in combination with an adjunct agent and/or a Lewisbase which is capable of providing a product of high molecular weightwhich is substantially linear and, optionally, which is capable ofpromoting copolymerization of olefin and functionalized olefin monomerunits.

SUMMARY OF THE INVENTION

The present invention is directed to certain late transition metalsalicylaldimine chelates as olefin polymerization catalysts, tobidentate ligand compounds of substituted salicylaldimine which areprecursors for said catalysts, to catalyst compositions composed of saidsalicylaldimine chelates in combination with an adjunct agent and/or aLewis base, the methods of forming said precursor compounds and saidcatalysts, and the method of polymerizing olefin monomers, especiallyethylene, as well as copolymerization of olefin and functionalizedolefin monomers. Each of the above elements of the present invention isfully described herein below.

DETAILED DESCRIPTION

The present invention provides a process for polymerizing olefinmonomers, in particular ethylene, in the presence of catalysts takenfrom the selected family of salicylaldimine late transition metalchelates and to catalyst compositions composed of said salicylaldiminechelates in combination with an adjunct agent and/or a Lewis base, toproduce polyolefins which can be substantially linear and have a weightaverage molecular weight of at least 1000.

It has been presently found that certain salicylaldimine late transitionmetal chelates can provide catalyst systems for the homopolymerizationof ethylene and copolymerization of ethylene and functionalized olefinsto provide high molecular weight, substantially linear polymer products.The catalyst of the present invention can be represented by thefollowing general formula:

wherein

R represents a C₁-C₁₁ alkyl, aryl, or substituted aryl provided z is 1when A is nitrogen and z is 0 when A is oxygen or sulfur;

R¹ represents a hydrogen atom, C₁-C₁₁ alkyl (preferably C₁-C₅ and mostpreferably tert-butyl); aryl, such as phenyl, biphenyl, terphenyl,naphthyl, anthracyl, phenanthracyl and the like; substituted arylwherein the substitution group is selected from C₁-C₆ alkyl,perfluoroalkyl, nitro, sulfonate, or halo group; arylalkyl, such astoluyl and the like; halo, such as chloro, bromo, and the like; nitrogroup; sulfonate group; siloxyl —OSiZ₃ where Z is selected from phenylor C₁-C₄ alkyl such as isopropyl or butyl and the like); or ahydrocarbyl terminated oxyhydrocarbylene group, —(BO)_(z)R⁷, whereineach B independently represents a C₁-C₄ (preferably C₂-C₃) alkylenegroup or an arylene group (preferably phenyl and especially the B groupadjacent to the basic structure to which the R¹ is bonded); R⁷represents a C₁-C₁₁ (preferably a C₁-C₃) hydrocarbyl group such as analkyl or an unsubstituted or substituted aryl group, such as phenyl,biphenyl, naphthyl and the like, alone or substituted with one or moreC₁-C₆ alkyl, and z is 1 to 4. R¹ is preferably a steric bulky groupselected from aryl, substituted aryl or a branched C₃-C₆ alkyl group oran alkoxyalkyl group and, most preferably, phenyl, anthracyl,phenanthracyl, terphenyl or t-butyl:

R² represents hydrogen atom, aryl, substituted aryl, C₁-C₁₁ alkyl,halogen atom or R¹ and R² can, together provide a hydrocarbylene orsubstituted hydrocarbylene which forms a carbocyclic ring which may benon-aromatic or aromatic; R² is preferably hydrogen or, taken with R¹ asa carbocyclic ring group:

R³ represents hydrogen:

R⁴ represents hydrogen atom, a C₁-C₁₁ alkyl, an aryl group such as aphenyl or a substituted aryl group such as 2,6-dimethylphenyl and thelike, and is preferably selected from hydrogen,

R⁵ represents a C₁-C₁₁ alkyl group (preferably a C₄-C₈ alkyl group) suchas methyl, ethyl, propyl, t-butyl, and the like, a cycloalkyl group suchas cyclohexyl and the like, an aryl group, such as phenyl, biphenyl,naphthyl and the like, or a substituted aryl having one or both orthopositions of the aromatic group (especially the phenyl group)substituted with a C₁-C₄ alkyl and/or the para position (with respect tothe N—R⁵ bond) substituted with a hydrogen atom, nitro, trifluoromethyl,halogen atom, methoxy, or C₁-C₄ alkyl or fused or unfused aryl,sulfonate, or a hydrocarbyl terminated oxyhydrocarbylene group—(BO)_(z)R⁷ as defined in R¹ above. R⁵ is preferably a t-butyl or acycloalkyl such as adamantyl, or a 2,6-di(C₁-C₄ alkyl)phenyl group andmost preferably 2,6-diisopropylphenyl or 2,6-diisopropyl-4-nitrophenyl:

R¹ and R⁵ can, together, form an oxyhydrocarbylene chain, e.g.,—(BO)_(m)B— wherein each B independently represents a C₁-C₄ alkylenegroup or an arylene group and m is an integer of from 2 to 5 preferably3-5;

n is an integer of 0 or 1;

R⁶ represents, when n is 1, an unsubstituted or substituted aromaticgroup, such as phenyl which is preferably unsubstituted, a C₁-C₁₁ alkyl(preferably a C₁-C₅ alkyl and most preferably methyl), a hydrogen atomor halogen atom (preferably chloro or bromo), or when n is 0, R⁶repesents an allyl or substituted allyl group wherein the substitutioncan be selected from a halogen atom, a nitro group or a sulfonate group:

L represents a coordination ligand such as triphenylphosphine, tri(C₁-C₆alkyl) phosphine, tricycloalkyl phosphine, diphenyl alkyl phosphine,dialkyl phenylphosphine, trialkylamine, arylamine such as pyridine,C₂-C₂₀ alkene such as octene, decene, dodecene, allyl and the like, asubstituted alkene wherein the substitution group may be selected from ahalogen atom (preferably chloro), an ester group, a C₁-C₄ alkoxy group,an amine group (—NR₂ wherein each R is hydrogen, or a C₁-C₃ alkyl),carboxylic acid or its alkali metal salt, di(C₁-C₃)alkyl ether,tetrahydrofuran, a nitrile such as acetonitrile and the like:

X represents any electron withdrawing group such as NO₂, halo (chloro,bromo and the like), persulfonate (SO₃ ⁻), sulfonyl ester (SO₂R),carboxyl (COO⁻), a perfluoroalkyl or a hydrogen atom. The sulfonate orcarboxylate is associated with an alkali or alkaline earth metal cation.Less preferably, X may represent an electron donating group such asalkoxy:

M represents one of the transition metals, that is a Group IV or VIIItransition metal selected from Fe, Co, Ni, Ru, Rh, Pd, Os, Ir, Pt in the+2 oxidation state or Ti, Zr, Hf in the +4 oxidation state andpreferably a late transition metal selected from iron, cobalt, nickel orpalladium and most preferably either nickel or palladium:

A represents oxygen, sulfur or nitrogen.

The present invention provides a catalyst which contains stericallybulky groups both above and below as well as within the plane oforientation with respect to the transition metal of the complex. It isbelieved, though not meant to be a limitation of the invention, that thesteric and electronic configuration of the presently achieved complexprovides the following desired characteristics:

(1) it utilizes late transition metals (preferably Ni or Pd) to providehigh resistance to deactivation by oxygenated species;

(2) it contains certain bidentate, chelating ligand groups which arebelieved to enhance the selectivity-controlling effect in thepolymerization of ethylene and of α-olefins;

(3) it contains groups of extreme steric bulk which provide shielding orpartial shielding of the axial faces of the transition metal squareplanar complexes and thereby it is believed, retards associativedisplacement and chain transfer during the polymerization;

(4) the steric bulk which is within the plane of the transition metalsquare planar complex may inhibit chain migration processes and therebycause substantially linear polymerization, and

(5) the steric bulk which is within the plane of the transition metalsquare planar complex may promote dissociation of the ancillary ligand,L, and thereby result in an increase in the number of activepolymerization sites.

The catalysts (I) are most preferably those having bulky substituents,such as aryl as, for example, terphenyl, anthracenyl, phenanthracenyland the like and substituted aryl groups such as 2,6-diisopropylphenyl,in the R¹ and/or R⁵ positions and further may have anelectron-withdrawing group in the X position or as a substituent of theR¹ and/or R⁵ group, preferably when such groups are aryl or substitutedaryl type groups.

The catalyst (I) of the present invention may further contain an etheror polyether group as part of structure of the subject salicylaldimineligand. The incorporation of such group(s) can be made at R¹ and/or atR⁵ or as an oxyhydrocarbylene chain between R¹ and R⁵ such that ahydrocarbon moiety of said oxyhydrocarbylene is directly bonded to thenitrogen atom at R⁵ and to the aromatic ring at R¹. Such catalystsprovide enhanced catalytic activity over catalyst (I) absent saidgroup(s) and do not need the use of adjunct agent or Lewis baseadditive, as described herein below.

Synthesis of the precursor ligands can be achieved by reacting theappropriate salicylaldehyde (having desired substituent groups on thephenyl ring) with a primary amine (R⁵NH₂), such as2,6-diisopropylaniline or 2,6-diisopropyl-4-nitroaniline and the like.The reaction can be carried out in solution, such as a C₁-C₅ alcohol(e.g. methanol, ethanol or the like) or aromatic compound (e.g.,benzene, toluene or the like). The reaction is preferably carried out attemperatures of from about 15° C. to 80° C. (most preferably at from 15to 25° C.) for a period of from one to twenty hours (most preferablyfrom 10 to 12 hours). The reaction is carried out at atmosphericpressure and in the presence of a catalytic amount of an organic acid,such as formic acid or acetic acid to provide the salicylaldimine ligand(IV) according to the equation below:

The bidentate ligand (IV) can be deprotonated using a lithium alkyl oran alkali metal hydride (e.g., NaH being preferred), as illustratedherein below) to form the alkali metal salt (V). The deprotonation iscarried out at low temperatures such as about 0° to 30° C. (preferably0° to 10° C.) at normal atmospheric pressure and in the presence of aninert solvent, such as tetrahydrofuran, dialkyl ether, C₅-C₁₀hydrocarbon, dioxane and the like. The reaction normally is completed ina short period, such as from about 5 to 30 minutes. The alkali metalsalt (V) can then be reacted with a late transition metal coordinationcompound of the type R⁶(L)₂MY, wherein each R⁶ and L are as definedabove, and Y represents a halogen atom, as for examplebis(triphenylphosphine) phenyl nickel chloride, and the like. Thisreaction may be conducted in an inert solvent, such as tetrahydrofuran,dialkyl ether, C₅-C₁₀ hydrocarbon, and the like at temperatures of fromabout 10 to 90° C. (preferably 10° to 30° C.) for periods of from one tofifteen hours (normally 10-15 hours) to provide catalyst (I) as follows:

R in formulas II and IV each independently represents hydrogen atom, aC₁-C₁₁ alkyl, aryl, or substituted aryl provided that R represents atleast one hydrogen atom and z is 1 when A is oxygen or sulfur and z is 2when A is nitrogen. R and z in formula V represents those groups asdefined with respect to formula I above. Each of the remaining symbolsR¹, R², R³, R⁴, R⁵, R⁶, M, Y, L and X represent the groups defined abovewith respect to catalyst I.

In the above, the R¹ may be hydrogen but preferably is a bulky groupwhich provides a steric shield of the transition metal's equatorial faceby being well-positioned in the plane of the transition metal complex aswell as some bulk in the axial face. For example, R¹ is preferably anaryl, such as phenyl, biphenyl, terphenyl, naphthyl, anthracenyl orphenanthracenyl, or nitro-substituted aryl, or a bulky alkyl, such as atert-butyl group. Such substituted salicylaldehydes (II) are readilyformed by formylation of an appropriately substituted phenol. This isconventionally accomplished by reacting the substituted phenol with analdehyde source, such as formaldehyde (e.g., paraformaldehyde,1,3,5-trioxane) or dimethylformamide in the presence of stannouschloride catalyst according to the procedures described by Casirighi etal in J. Chem. Soc. Perkins Trans. I, 1980, 1862-5, the teachings ofwhich are incorporated herein by reference in its entirety.

As indicated above, R¹ may be selected from sterically bulky groupsother than hydrocarbyl groups as, for example, siloxane groups. Suchsubstitution can be readily accomplished by using2,3-dihydroxybenzaldehyde as the starting material II to form the Schiffbase aldimine compound IV. The 3-position hydroxyl group can then beconverted to a siloxy group by reaction with the appropriate aryl, alkylor mixed substituted silyl halide as, for example triisopropyl silylchloride, diphenyl-t-butyl silyl chloride, triphenyl silyl chloride andthe like. Deprotonation and reaction with transition metal coordinationcompound of the type R⁶(L)₂MY provides the desired catalyst compound Iin the manner described above.

As defined above, R¹ and R⁵ may each independently be selected from ahydrocarbyl terminated oxyhydrocarbylene containing group. Such groupsmay be represented as —(BO)_(z)R⁷ wherein each B independentlyrepresents a C₁-C₄ (preferably a C₂-C₃) alkylene group or an arylenegroup and R⁷ represents a C₁-C₁₁, (preferably C₁-C₃) hydrocarbyl groupsuch as alkyl, an aryl, an alkaryl, or an aralkyl group and z representsan integer of 1 to 4. Such oxyhydrocarbylene group may be made part ofcompound I by mono-alkylation of 2,2′-dihydroxybiphenyl at one OH groupwith bromoethyl ether, followed by formylation (with an aldehyde source)of the other phenolic ring adjacent to the OH, followed by imineformation and finally metallation with R⁶(L)₂MY in the manner describedpreviously.

Further, it has been found that desired catalyst can be in the form ofcompound (I) when the aryl group is substituted with an electronwithdrawing group X, as defined above. For example, the salicylaldehydemay be substituted with a nitro, halo, trifluoromethyl, sulfonate,sulfonyl or carboxyl group in the 5-position. Some of the substitutedsalicylaldehydes are commercially available. They may be further reactedwith the substituted aniline or aniline derivative as described above toprovide the bidentate ligand IV. The ligand is then formed into thetransition metal complex I, in the manner described above.

It has been found that substituted salicylaldimine complexes of latetransition metals described above provide catalytic activity for olefin(e.g., ethylene) polymerization and provide substantially linear producthaving a low degree of branching. These complexes are neutral compoundsand, as such do not require the presence of organo aluminum or partiallyhydrolyzed organo aluminum compounds or other reducing agent to causeactivation of the complex towards olefin insertion reaction andpolymerization. However, organo aluminum and hydrolyzed organo aluminumcompounds, such as methyl alumoxane or trialkyl aluminum compounds andthe like, may be present and are preferably present when R⁶ is halogen.Compounds I are a new family of complexes of single-site catalysts.

The subject catalysts may be used as the sole catalyst (this isespecially acceptable when the bulky group R¹ is large such as phenyl,biphenyl, terphenyl, anthracenyl, phenanthracenyl, nitro-substitutedaryl or the like) or may be used in combination with an adjunct agentand/or a Lewis base (preferred). The adjunct agent comprises knownphosphine sponge material capable of facilitating phosphine (ligand L)dissociation and trapping of free phosphine. Such catalyst compositionadjunct agents are, for example, bis(cyclooctadiene)-nickel,tris(pentafluorophenyl) boron, 9-borabicyclo[3.3.1]nonane (9-BBN),methyl iodide, and the like.

It has unexpectedly been found that the subject catalyst provides anenhanced catalyst composition when combined with a Lewis base as, forexample ethers, esters, aldehydes, ketones, alcohols, amides, organiccarbonates, organonitro compounds, or mixtures thereof and even water.It is commonly believed that organometallic catalysts should be combinedwith Lewis acid compounds to provide effective catalyst systems and thatwater acts as a poison to such catalysts. In contrast to the presentfinding, it has been previously deemed important to use conventionalsingle site catalysts, such as metallocene catalysts, in the absence ofmoisture or other oxygenated compounds in order to provide an effectivecatalyst system.

The Lewis base additives found useful in forming a catalyst compositionwith the catalyst of compound I or V comprise ether compounds, such asdialkyl ethers where each alkyl group is independently selected from aC₁-C₁₈ alkyl, preferably a C₁-C₅ alkyl group as, for example, diethylether, methyl ethyl ether, diisopropyl ether, ethyl propyl ether,dibutyl ether and the like; vinyl ethers as, for example, ethyl vinylether; aryl ethers as, for example, dibenzyl ether, diphenyl ether,dinaphthyl ether and the like, mixed ethers as, for example, amyl phenylether, methyl benzohydryl ether, benzyl phenyl ether, anisole, phenetoleand the like. The ether additive may also be selected from cyclic ethersas, for example, tetrahydrofuran, dioxane-1,4, dioxane-1,3, crown etherssuch as 18-crown-6, 14-crown-5, 12-crown-4 and the like as well aspolyethers such as dimethoxyethane, diglyme, triglyme, pentaglyme, orpolyoxyalkylenes as, for example, polyoxyethylene (preferably lowermolecular weight polymers which are miscible in the polymerizationsolvent used).

The above ethers, especially the alkyl and/or aryl group containingethers and cyclic ethers described above, and most preferably dialkylether (diethyl ether) and low molecular weight polyethers (dimethoxyethane), have been found to be effective solvents or co-solvents for usein the polymerization process when the subject catalyst of compound I orcompound V is used, as described herein below.

The Lewis base may be selected from an organic ester represented by theformula

wherein each R⁹ is independently selected from a C₁-C₁₁ alkyl group,preferably a C₁-C₅ alkyl group as, for example, ethyl acetate, propylacetate, hexyl acetate, ethyl butyrate, propyl butyrate, ethyl caproate,ethyl caprylate, ethyl laurate and the like.

Further, aldehydes and ketones have been found useful as a Lewis baseadditive in forming the subject catalyst composition. They may berepresented by the formula

wherein R¹⁰ represents a C₁-C₁₂ hydrocarbyl selected from unsubstitutedor substituted (e.g., carbonyl) alkyl, aryl, alkaryl or aralkyl groupsand R¹¹ represents a hydrogen atom or an R¹⁰ group, which isindependently selected. For example, the aldehyde or ketone may beselected from acetone, propanone, butyrone, 4-heptanone,2,4-pentanedione and the like, as well as cyclic ketones such ascyclohexanone, 1,4-cyclohexanedione and the like, or an aldehyde such asacetaldehyde, capraldehyde, valeraldehyde and the like.

Still further, an alcohol can be used as the Lewis base additive informing the subject catalyst composition. They may be selected frommonohydric or polyhydric alcohols including, for example, alcoholshaving hydrocarbyl moiety composed of a C₁-C₁₂ (preferably C₁-C₃) alkyl,aryl (e.g., phenyl or benzyl), alkaryl and aralkyl groups. Examples ofsuch alcohols include methanol, ethanol, propanol, isopropanol, butanol,t-butanol, 2-pentanol, 3-hexanol, glycol, 1,2,3-propanetriol, phenol,phenethyl alcohol, para-methyl phenol and the like.

Amides can be used as the Lewis base additive in forming the subjectcatalyst composition. The amides may be represented by the formula

wherein R¹² and R¹³ each independently represent a C₁-C₁₁, hydrocarbyl,R¹⁴ represents hydrogen or a C₁-C₁₁ hydrocarbyl. R¹³ and R¹⁴ are,preferably, independently selected from a C₁-C₃ alkyl group.

Nitroalkanes and nitroaromatics have also been found to be useful as aLewis base additive in forming the subject catalyst composition. Thenitroalkanes may be a mono (preferred) or poly nitro compound formedwith a C₁-C₁₁ (preferably a C₁-C₃) alkyl group. The aromatic nitroshould be a mono nitro compound such as nitrobenzene and the like.

It has been unexpectedly found that the subject catalyst composition maycontain small amounts of water and that the presence of water does notdestroy the activity of the catalyst of the subject invention. Thus,unlike most organometallic catalysts useful in olefin polymerization,the presently described catalyst can be used in the presence of smallamounts of moisture to provide a catalyst composition which can remainactive in the polymerization of olefins or mixtures of olefins andfunctional olefin monomer(s).

The amount of the Lewis base (except water) additive can besubstantially any amount desired with from 10⁰ to 10⁴ times the amountof compound I or V on a molar basis being preferred and most preferred,from 10¹ to 10³ times the molar amount of catalyst when ether or lowmolecular weight polyether is the Lewis base used and from 10⁰ to 10²the molar amount of catalyst when other Lewis bases are used. In thecase of water, the molar ratio of water to compound I or V which may bepresent can range from 0 to about 10², preferably from 0 to 10¹.

This invention concerns processes for making polymers, comprising,contacting the subject catalyst composition with one or more selectedolefins or cycloolefins, alone or optionally with a functional α-olefinsuch as a carboxylic acid of the formula CH₂═CH(CH₂)_(m)COOH, acarboxylic acid ester of the formula CH₂═CH(CH₂)_(m)CO₂R⁷ orCH₂═CHOCOR⁷, an alkyl vinyl ether of the formula CH₂═CH(CH₂)_(m)OR⁷,vinyl ketones of the formula CH₂═CH(CH₂)_(m)C(O)R⁷, a vinyl alcohol ofthe formula CH₂═CH(CH₂)_(m)OH, or a vinyl amine of the formulaCH₂—CH(CH₂)_(m)NR⁸ ₂, wherein m is an integer of 0 to 10 and R⁷ is aC₁-C₁₀ hydrocarbyl group, aryl or substituted aryl group (preferablymethyl) and R⁸ is independently selected from hydrogen or an R⁷ group; afunctional cycloolefin, such as functionalized norbornene wherein thefunctional group is an ester, alcohol, carboxylic acid, halogen atom, aprimary, secondary or tertiary amine group or the like; or unsaturateddicarboxylic acid anhydride or carbon monoxide or the like and otherselected monomers such as vinyl halides. The “polymerization process”described herein (and the polymers made therein) is defined as a processwhich produces a polymer with a molecular weight (Mw) of at least about1000.

The subject catalysts may generally be written as

wherein each symbol R, R¹, R², R³, R⁴, R⁵, R⁶, L, M, A and X are definedabove. Preferably M is Ni(II) or Pd(II).

Alternately, the catalytic polymerization of the present invention canbe carried out by contacting one or more selected olefins orcycloolefins alone or optionally with a functional olefin monomer, asdescribed above with a catalyst composition formed in-situ and composedof one or more bidentate ligand (V) described above in combination witha transition metal (M) organic complex, R⁶(L)₂MY. The ligand (V) andcomplex should be used in about a 1:1 molar ratio. In a preferredembodiment of the present invention, the bidentate ligand V is combinedwith a transition metal organic complex of the formula R⁶(L)₂MY in abouta 1:1 molar ratio in the presence of olefin and/or cycloolefin alone oroptionally with a functional olefin monomer. The catalyst compositioncomposed of ligand (V) and transition metal organic complex may furthercontain a phosphine sponge and/or a Lewis base additive, such as thosedescribed above, or an organo aluminum or hydrolyzed organo aluminumcompound or mixtures thereof as described above with respect to catalystcompositions composed of compound (I) which have a halogen as R⁶.

In all catalysts and precursor bidentate ligands, described herein, itis preferred that R¹ and R⁵ are each independently a sterically bulkyhydrocarbyl. In one form it is especially preferred that R¹ and R⁵ areeach independently aryl or substituted aryl groups. In another form, itis preferred that R¹ and/or R⁵ be independently selected from ahydrocarbyl terminated oxyhydrocarbylene containing group, as describedabove. It is also preferred that R¹ and R² are each taken together toprovide a hydrocarbylene which forms a carbocyclic ring. It is furtherpreferred that X, when present, be an electron-withdrawing group such asnitro, trifluoromethyl, sulfonate, sulfonyl or carboxylate and the likesthereof. It is preferred that when R⁵ is a substituted aryl, the 4position of the aryl (with respect to the N— bond) be either hydrogen ornitro.

When using I or V as a catalyst in the manner described above, it ispreferred that R², R³ and R⁴ are hydrogen or methyl, unless R² is, whentaken together with R¹, a C₄-C₁₀ carbocyclic group which may or may notbe aromatic. It is also preferred that either or both R¹ and R⁵ arebiphenyl, terphenyl, anthracenyl, phenanthracenyl,2,6-diisopropylphenyl, 2,6-dimethylphenyl, 2,6-diethylphenyl,4-methylphenyl, 2-isopropyl-6-methylphenyl, phenyl,2,4,6-trimethylphenyl, 2-t-butylphenyl, 2-t-butyl-4-methylphenyl,2,6-diisopropyl-4-nitrophenyl, and 10-nitroanthracenyl.

The structure of the ligand associated with compound I or compound V mayinfluence the polymer microstructure and polymer molecular weight. Forexample, it is preferred that R¹ be a bulky aryl or substituted arylgroup. Complexes with R¹ of this type generally produce higher molecularweight and more linear polymer product for any given set of conditions.The catalyst or the catalyst composition of I or V with the phosphinesponge adjunct and/or organo aluminum compound adjunct, or with theLewis base additive or mixtures of adjunct and Lewis base whenoptionally used, are contacted, usually in the liquid phase, withethylene or other olefin (RCH═CH₂), and/or 4-vinylcyclohexane,4-vinylcyclohexene, cyclopentene, cyclobutene, substituted norbornene,or norbornene. The liquid phase may include a compound added just as asolvent and/or may include the monomer(s) itself and/or may comprise theLewis base (especially an ether compound) in the liquid phase atreaction conditions. When an adjunct is used, the molar ratio of adjunctto compound I or V is from about 0.001:1 to 15:1, preferably about0.01:1 to about 8:1, and most preferably from 0.1:1 to 3:1. Thetemperature at which the polymerization is carried out is from about−100° C. to about +200° C., preferably about −20° C. to about +100° C.and most preferably between about 0° C. and 90° C. All ranges oftemperatures being covered by this teaching. The pressure at which thepolymerization is carried out is not critical, atmospheric pressure toabout 100 MPa, or more, being a suitable range. The pressure may affectthe yield, molecular weight and linearity of the polyolefin produced,with increased pressure providing more linear and higher molecularweight polymer product.

Preferred alpha-olefins and cyclic olefins in the polymerization are oneor more of ethylene, propylene, 1-butene, 2-butene, 1-hexene, 1-octene,1-pentene, 1-tetradecene, norbornene, and cyclopentene, with ethylene,propylene, cyclopentene and norbornene being more preferred. Ethylene(alone as a monomer) is especially preferred.

The polymerization may be run in the presence of various liquids. Thesolvent in which the polymerization may be conducted can be selectedfrom (i) the monomer(s), per se or (ii) any organic compound which isliquid under the reaction conditions and is substantially inert to thereactants and product, or (iii) a Lewis base additive (except waterwhich, when used, should be present in limited amounts) which is liquidunder the reaction conditions, or mixtures thereof. Particularlypreferred are aprotic organic liquids or organic ethers or mixturesthereof. The catalyst system, monomer(s), and polymer may be soluble orinsoluble in these liquids, but obviously these liquids should notprevent the polymerization from occurring. Suitable liquids includealkanes, cycloalkanes, halogenated hydrocarbons, ethers, and aromaticand halogenated aromatic hydrocarbons. Specific useful solvents includehexane, heptane, toluene, xylenes, and benzene, methylene chloride,ethyl ether, dimethoxyethane, tetrahydrofuran and crown ethers.

The catalyst compositions of the present invention cause polymerizationof one or more alpha-olefin, with functional olefins such as thosedescribed herein above. When carbon monoxide is used as a comonomer, itforms alternating copolymers with the various alpha-olefins. Thepolymerization to form the alternating copolymers is carried out withboth CO and the olefin simultaneously present in the process mixture,and in the presence of the present catalyst composition.

The catalyst of the present invention may also be supported on a poroussolid material (as opposed to just being added as a suspended solid orin solution), for instance on silica gel, zeolite, crosslinked organicpolymers such as styrene-divinylbenzene copolymer and the like. Bysupported is meant that the catalyst may simply be carried physically onthe surface of the porous solid support, may be adsorbed, or may becarried by the support by other means.

In many of the polymerizations, certain general trends may occur,although for all of these trends there are exceptions. Pressure of themonomers (especially gaseous monomers such as ethylene) has an effect onthe polymerizations in many instances. Higher pressure often reducesbranching and extends polymer chain length, especially in ethylenecontaining polymers. Temperature also affects these polymerizations.Higher temperature usually increases branching.

In general, the period of time during which the catalysts of compound Ior the catalyst composition having compound V remains active can beextended greatly based on a particular ligand structure, polymerizationtemperature, or type of Lewis present. Catalyst lifetime is long whenLewis base such as ether or dimethyoxyethane is present, co-catalystadjunct is absent, and R¹ is a bulky aryl or substituted aryl group.

When the polymer product of the present invention is a copolymer offunctionalized group containing monomer, the functional group may befurther used to cross-link the polymer. For example, when copolymers ofan olefinic carboxylic acid or olefinic ester and an alpha-olefin aremade, they may be crosslinked by various methods known in the art,depending on the specific monomers used to make the polymer. Forinstance, carboxyl or ester containing polymers may be crosslinked byreaction with diamines or with diisocyanates to form bisamides. Thecarboxyl groups may also be neutralized with a monovalent or divalentmetal containing base (e.g., NaOH, CaO) to form ionomeric orpseudo-crosslinked polyolefin copolymer.

The resultant polymers formed according to the present invention,especially those of ethylene homo or copolymers may have varying degreesof branching in the polymer. Branching may be determined by NMRspectroscopy (see the Examples for details), and this analysis candetermine the total number of branches, the branching distribution andto some extent the length of the branches. Herein the amount ofbranching is expressed as the number of branches per 1000 of the totalmethylene (—CH₂—) groups in the polymers, with one exception. Methylenegroups that are in an ester grouping, i.e., —CO₂R; a ketone group, i.e.,—C(O)R are not counted as part of the 1000 methylenes. For example,ethylene homopolymers have a branch content of about 0 to about 150branches per 1000 methylene groups, preferably about 5 to about 100 andmost preferably about 3 to about 70 branches per 1000 methylene groups.These branches do not include polymer end groups. Alternately, branchcontent can be estimated from correlation of total branches asdetermined by NMR with polymer melting point as determined bydifferential scanning calorimetry.

The polymers formed by the present invention may be mixed with variousadditives normally added to elastomers and thermoplastics [see EPSE(below), vol. 14, p. 327-410] which teaching is incorporated herein byreference. For instance reinforcing, non-reinforcing and conductivefillers, such as carbon black, glass fiber, minerals such as silica,clay, mica and talc, glass spheres, barium sulfate, zinc oxide, carbonfiber, and aramid fiber or fibrids, may be used. Antioxidants,antiozonants, pigments, dyes, slip agents, antifog agents, antiblockagents, delusterants, or compounds to promote crosslinking may be added.Plasticizers such as various hydrocarbon oils may also be used.

The polymers formed by the present invention may be used for one or moreof the applications listed below. In some cases a reference is givenwhich discusses such uses for polymers in general. All of thesereferences are hereby included by reference. For the references, “U”refers to W. Gerhartz, et al., Ed., Ullmann's Encyclopedia of IndustrialChemistry, 5th Ed. VCH Verlagsgesellschaft mBH, Weinheim, for which thevolume and page number are given, “ECT3” refers to the H. F. Mark, etal., Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., JohnWiley & Sons, New York, “ECT4” refers to the J. I. Kroschwitz, et al.,Ed., Kirk-Othmer Encyclopedia of Chemical Technology, 4th Ed., JohnWiley & Sons, New York, for which the volume and page number are given.“EPST” refers to H. F. Mark, et al., Ed., Encyclopedia of PolymerScience and Technology, 1st Ed., John Wiley & Sons, New York, for whichthe volume and page number are given, “EPSE” refers to H. F. Mark, etal., Ed., Encyclopedia of Polymer Science and Engineering, 2nd Ed., JohnWiley & Sons, New York, for which volume and page numbers are given, and“PM” refers to J. A. Brydson, ed., Plastics Materials, 5th Ed.,Butterworth-Heinemann, Oxford, UK, 1989, and the page is given. In theseuses, a polyethylene, polypropylene and a copolymer of ethylene andpropylene are preferred.

1. The polyolefins herein are especially useful in blown filmapplications because of their particular rheological properties (EPSE,vol. 7, p. 88-106). It is preferred that these polymers have somecrystallinity.

2. The polymers are useful for blown or cast films or as sheet (seeEPSE, vol. 7 p. 88-106; ECT4, vol. 11, p 843-856; PM, p. 252 and p.432ff). The films may be single layer or multilayer, the multilayerfilms may include other polymers, adhesives, etc. For packaging thefilms may be stretch-wrap, shrink-wrap or cling wrap and may also beheat sealable. The films are useful for many applications such aspackaging foods or liquids, geomembranes and pond liners. It ispreferred that these polymers have some crystallinity.

3. Extruded films or coextruded films may be formed from these polymers,and these films may be treated, for example by uniaxial or biaxialorientation after crosslinking by actinic radiation, especially electronbeam irradiation. Such extruded films are useful for packaging ofvarious sorts. The extruded films may also be laminated to other filmsusing procedures known to those skilled in the art. The laminated filmsare also useful for packaging of various sorts.

4. The polymers, particularly the elastomers, may be used as toughenersfor other polyolefins such as polypropylene and polyethylene.

5. Tackifiers for low strength adhesives (U, vol. A1, p 235-236) are ause for these polymers. Elastomers and/or relatively low molecularweight polymers are preferred.

6. An oil additive for smoke suppression in single-stroke gasolineengines is another use. Elastomeric polymers are preferred.

7. The polymers are useful as base resins for hot melt adhesives (U,vol. A1, p 233-234), pressure sensitive adhesives (U, vol. A1, p235-236) or solvent applied adhesives. Thermoplastics are preferred forhot melt adhesives.

8. Base polymer for caulking of various kinds is another use. Anelastomer is preferred. Lower molecular weight polymers are often used.

9. Wire insulation and jacketing may be made from any of the polyolefins(see EPSE, vol. 17, p. 828-842). In the case of elastomers it may bepreferable to crosslink the polymer after the insulation or jacketing isformed, for example by free radicals.

The following examples are provided herein below for illustrativepurposes only and are not meant to be a limitation on the scope of theinvention. All parts and percentages are by weight unless otherwiseindicated.

EXAMPLE I HOC₆H₄-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a methanol (25 mL) solution of salicylaldehyde (10 g, 82 mmol) wasadded formic acid (1 mL) and 2,6-diisopropylaniline (21 g, 120 mmol).The resulting mixture was stirred for 1 hour. After this time, a yellowsolid precipitated out of solution. The solid was collected byfiltration through a glass frit and washed with methanol (2×10 mL) toyield 21 g (90%) of a yellow solid. ¹H NMR (C₆D₆): δ 1.24 (d, 12H,J_(HH)=6.94 Hz), 3.07 (septet, 2H, J_(HH)=6.94 Hz), 7.02-7.48 (m, 7H),8.39 (s, 1H), 13.12 (s, 1H); ¹³C NMR (C₆D₆): δ 23.5, 28.2, 117.2, 119.1,123.3, 125.6, 132.5, 133.3, 138.8, 146.4, 161.3, 167.0.

EXAMPLE II [OC₆H₄-o-C═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product of Example I(0.59 g, 1.5 mmol) and bis(triphenylphosphine)nickel(phenyl)chloride(1.0 g, 1.44 mmol) in benzene (20 mL). The reaction was stirred at roomtemperature for 1 hour. After this time, the reaction was filtered bycannula filtration, and the filtrate was concentrated in vacuo to ˜5 mL.Pentane (30 mL) was added to the reaction. A yellow-orange solidprecipitated from solution, and was isolated by cannula filtration toyield 0.74 g (76%) of a yellow-orange solid. ¹H NMR (C₆D₆): δ 1.03 (d,6H, J_(HH)=6.84 Hz), 1.29 (d, 6H, J_(HH)=6.84 Hz), 4.05 (septet, 2H,J_(HH)=6.84 Hz), 6.31-7.69 (m, 27H), 7.93 (d, 1H, J_(HP)=8.80 Hz); ¹³CNMR (C₆D₆): δ 22.6, 25.5, 28.8, 117.4, 120.0, 122.8, 125.3, 126.2,128.3, 128.6, 129.7, 130.5, 131.0, 131.5, 133.3, 133.8, 134.0, 134.4 (d,J_(CP)=9.77 Hz), 137.4, 140.1, 149.4, 159.6, 165.2; ³¹ P NMR (C₆D₆): δ25.94. Anal. Calcd for C₄₃H₄₂NNiOP: C, 76.35; H, 6.25; N, 2.07. Found:C, 76.20; H, 6.64; N, 1.89.

EXAMPLE III HO-(3-t-Bu)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a methanol (25 mL) solution of t-butylsalicylaldehyde (10 g, 82 mmol)was added formic acid (1 mL) and 2,6-diisopropylaniline (21 g, 120mmol). The resulting mixture was refluxed for 10 hours. After this time,the methanol was removed by rotary evaporation to yield a dark-brownoil. The oil was loaded onto a silica gel column and eluted with 90:10hexane:ethyl acetate to yield 24 g (90%) of a viscous, orange oil. ¹HNMR (C₆D₆): δ 1.24 (d, 12H, J_(HH)=6.85 Hz), 1.56 (s, 9H), 3.10 (septet,2H, J_(HH)=6.85 Hz), 6.94-7.49 (m, 6H), 8.39 (s, 1H), 13.71 (s, 1H); ¹³CNMR (C₆D₆): δ 23.5, 28.2, 34.9, 118.3, 118.6, 123.3, 125.4, 130.5,130.8, 137.6, 139.0, 146.4, 160.7, 167.6.

EXAMPLE IV HO-(3-Ph)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a methanol (15 mL) solution of 6-phenyl salicylaldehyde (2.4 g, 12mmol) was added formic acid (0.50 mL) and 2,6-diisopropylaniline (2.8 g,16 mmol). The resulting mixture was refluxed for 10 hours. After thistime, the methanol was cooled to room temperature at which time yellowcrystals precipitated from the solution. The crystals was collected byfiltration and washed with methanol (2×10 mL) to yield 3.0 g (70%) of ayellow solid. ¹H NMR (C₆D₆): δ 1.01 (d, 12H, J_(HH)=6.88 Hz), 2.96(septet, 2H, J_(HH)=6.88 Hz), 7.05-7.74 (m, 11H), 7.92 (s, 1H), 13.90(s, 1H); ¹³C NMR (C₆D₆): δ 23.5, 28.5, 119.2, 119.3, 123.5, 125.9,127.4, 127.7, 129.9, 130.8, 131.9, 134.7, 138.0, 138.9, 146.8, 159.4,167.6.

EXAMPLE V [O-(3-t-Bu)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product of ExampleIII (2.1 g, 4.8 mmol) and bis(triphenylphosphine)nickel(phenyl)chloride(3.1 g, 4.40 mmol) in THF (50 mL). The reaction was stirred at roomtemperature for 1.5 hours. After this time, the reaction was filtered bycannula filtration and the filtrate was concentrated in vacuo to 5 mL.Pentane (30 mL) was added with vigorous stirring and the reaction wascooled at −78° C. A yellow-orange solid precipitated from solution, andwas isolated by cannula filtration to yield 3.5 g (83%) of ayellow-orange solid. ¹H MNR (C₆D₆): δ 0.93 (s, 9H), 1.08 (d, 6H,J_(HH)=5.88 Hz), 1.22 (d, 6H, J_(HH)=5.88 Hz), 4.28 (septet, 2H,J_(HH)=5.88 Hz), 6.21-7.83 (m, 26H), 7.97 (d, 1H, J_(HP)=9.12 Hz); ¹³C(C6D₆): δ 22.7, 25.5, 28.9, 29.8, 34.6, 113.9, 120.2, 121.0, 122.8,125.0, 125.9, 128.3, 128.5, 129.1, 129.7, 131.5, 131.8, 132.2, 133.3,134.9 (d, J_(CP)=10.4 Hz), 137.0, 140.8, 141.9, 150.2, 166.1, 166.8; ³¹PNMR (C₆D₆): δ 23.35. Anal. Calcd for C₄₇H₅₀NNiOP: C, 77.06; H, 6.88; N,1.91. Found: C, 76.93; H, 6.81; N, 1.63.

EXAMPLE VI [O-(3-Ph)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product of ExampleIV (0.56 g, 1.6 mmol) and bis(triphenylphosphine)nickel(phenyl)chloride(1.0 g, 1.4 mmol) in benzene (20 mL). The reaction was stirred at refluxfor 1 hour. After this time, the reaction was filtered by cannulafiltration and the filtrate was concentrated in vacuo to ˜5 mL. Pentane(30 mL) was added to the vigorously stirred solution. A light-greensolid precipitated from solution, and was isolated by cannula filtrationto yield 0.84 g (89%) of a yellow-orange solid. ¹H NMR (C₆D₆): δ 1.12(d, 6H, J_(HH)=6.56 Hz), 1.21 (d, 6H, J_(HH)=6.56 Hz), 3.3 (s, 3H), 4.11(septet, 2H, J_(HH)=6.56 Hz), 3.29 (s, 3H), 6.18-7.80 (m, 31H), 7.99 (d,1H, J_(HP)=9.52 Hz); ¹³C NMR (C₆D₆): δ 22.6, 25.6, 28.9, 114.4, 119.8,121.1, 122.7, 125.0, 126.0, 127.4, 128.6, 129.4, 129.6, 131.7, 132.1,134.0, 134.3, 134.4 (d, J_(CP)=9.76 Hz), 135.3, 136.8, 137.8, 140.1,140.7, 150.0, 163.7, 166.5; ³¹P NMR (C₆D₆): δ 621.87. Anal. Calcd forC₄₉H₄₆NNiOP: C, 78.20; H, 6.16; N, 1.86. Found: C, 77.69; H, 6.36; N,1.42.

EXAMPLE VII 2-(9-Phenanthrene)phenol-tetrahydropyran Adduct

A solution of tetrahydropyran-protected phenol (10 g, 56 mmol) indiethyl ether (100 mL) was treated at room temperature with BuLi (44 mL,70 mmol) for 4.5 hours. A solution of MgBr₂ was separately prepared byslowly adding 1,2-dibromoethane (5.3 mL, 62 mmol) to Mg turnings (1.6 g,67 mmol) in diethyl ether (100 mL), and stirred for 4 hours. The Li-saltwas added via cannula to the MgBr₂ solution to form the Grignardreagent. This solution was added to a cooled solution (−78° C.) of9-bromophenanthrene (9.7 g, 38 mmol) andNiCl₂(diphenylphosphinoethylene) (0.62 g, 1.2 mmol). The mixture wasslowly warmed to room temperature and heated at reflux overnight. Afterthis time, the reaction mixture was poured through a short silica gelcolumn with 1:1 dichloromethane:hexane. The solvent was removed undervacuum to leave an orange, viscous oil. The yield of crude product was14 g (70%). ¹H NMR (CDCl₃): δ 1.02-1.48 (m, 6H), 3.75 (m, 2H), 5.42 (d,1H, J_(HH)=8.40 Hz), 7.20-8.81 (m, 13H); ¹³C NMR (C₆D₆): δ 17.7, 18.3,25.2, 30.1, 61.6, 62.0, 96.3, 96.9, 115.1, 115.4, 121.8, 121.9, 122.7,126.1, 126.2, 126.3, 126.5, 126.7, 128.7, 129.2, 129.3, 130.1, 130.2,130.5, 130.6, 131.5, 131.6, 131.7, 131.9.

EXAMPLE VIII 2-(Phenanthrene)salicylaldehyde

To a solution of 2-(9-phenanthrene)phenol (6.8 g, 25 mmol) and2,6-lutidine (4.6 g, 43 mmol) in toluene (50 mL) was slowly added SnCl₄(0.75 mL, 6.4 mmol). The solution was stirred at room temperature for 20minutes. Paraformaldehyde was added (4.3 g, 140 mmol) and the reactionwas stirred at 110° C. for 12 hours. After cooling to room temperature,the reaction mixture was poured into water (30 mL), and adjusted to pH 1with concentrated HCl. The mixture was extracted with diethyl ether (500mL), and the organic layer was washed twice with sat. brine and driedover Na₂SO₄. The solvent was removed by rotary evaporation to leave ayellow oil. The oil was loaded onto a silica gel column and eluted with9:1 hexane:ethyl acetate. The yield of product was 1.9 g (26%). ¹H NMR(CDCl₃): δ 7.21-8.78 (m, 12H), 10.02 (s, 1H), 11.32 (s, 1H); ¹³C NMR(C₆D₆): δ 120.0, 120.6, 122.7, 123.0, 126.6, 126.9, 127.0, 128.5, 128.8,130.5, 130.8, 131.5, 133.8, 139.1, 159.6, 196.9.

EXAMPLE IX HO-3-(9-Phenanthrene)C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂

2-(9-Phenanthrene)salicylaldehyde (1.9 g, 6.4 mmol),2,6-diisopropylaniline (1.4 g, 7.9 mmol), and p-toluenesulfonic acid (65mg, 0.34 mmol) was dissolved in benzene (27 mL). The solution wasstirred at reflux overnight. After this time, the benzene was removedunder vacuum. To the resulting oil was added hexane (100 mL) undervigorous stirring at which time a white solid precipitated. The solidwas collected by filtration through a glass frit. A second crop ofproduct was obtained from the filtrate to yield 1.7 g (58%). ¹H NMR(CDCl₃): δ 1.22 (d, 12H, J_(HH)=6.90 Hz), 3.07 (septet, 2H, J_(HH)=6.90Hz), 7.14-8.90 (m, 15H), 8.46 (s, 1H), 13.45 (s, 1H); ¹³C NMR (C₆D₆): δ23.8, 28.2, 119.0, 122.7, 123.0, 123.4, 125.0, 126.6, 126.8, 127.2,128.5, 128.9, 129.3, 130.4, 130.6, 131.2, 131.7, 132.2, 135.6, 138.9,159.3, 166.9.

EXAMPLE X 2-(Anthracene)phenol-tetrahydropyran Adduct

In a three-necked, 250 mL flask under an atmosphere of Ar was added Mgturnings (2.1 g, 87 mmol) in THF (20 mL). A few drops of1,2-dibromoethane was added to activate the Mg. Then a solution of thetetrahydropyran-protected 2-bromophenol (22 g, 87 mmol) in THF (70 mL)was added dropwise, and the reaction was stirred at reflux overnight.After this time, the resulting slurry was added by cannula to a solutionof 9-bromoanthracene (22 g., 88 mmol) and NiCl₂(dppe) (1.4 g, 2.6 mmol)in THF (175 mL). The resulting solution was heated at reflux for 4 days.After this time, the solvent was removed in vacuo, and the oily residuewas chromatographed on a silica gel column with 90:10 hexane:ethylacetate. Removal of solvent yielded 10 g (34%) of a white crystallinesolid. ¹H NMR (CDCl₃): δ 0.87-1.30 (m, 6H), 3.42 (m, 1H), 3.60 (m, 1H),5.30 (s, 1H), 7.25-8.49 (m, 13H); ¹³C NMR (C₆D₆): δ 17.7, 24.9, 30.0,61.6, 61.9, 96.1, 96.4, 115.3, 115.8, 121.4, 121.7, 124.7, 125.2, 126.0,126.6, 127.1, 127.5, 127.8, 128.2, 128.6, 129.0, 130.2, 130.3, 131.3,132.5, 132.9, 133.9, 155.4.

EXAMPLE XI 2-(Anthracene)salicylaldehyde-tetrahydropyran Adduct

To a diethyl ether (250 mL) solution of the tetrahydropyran-protectedadduct of 2-(9-anthracene)phenol was added n-BuLi (28 mL, 43 mmol)dropwise. The resulting solution was stirred at room temperature for 4.5hours. After this time, the solution was cooled to −78° C. and dimethylformamide (5.4 mL, 70 mmol) was added to the reaction, which was allowedto warm to room temperature. After this time, the reaction was quenchedwith H₂O and extracted with diethyl ether (200 mL). The organic layerwas separated and dried with Na₂SO₄. The solvents were removed by rotaryevaporation to yield a yellow solid. The solid was washed with hexane(50 mL) and dried in vacuo to yield 5.0 g (60%) product. ¹H NMR (CDCl₃):δ 0.56-1.97 (m, 6H), 2.89 (m, 1H), 3.48 (m, 1H), 4.27 (m, 1H), 7.46-8.10(m, 13H), 8.57 (s, 1H), 10.62 (s, 1H); ¹³C NMR (C₆D₆): δ 19.5, 24.6,29.9, 64.2, 102.4, 124.6, 125.5, 126.1, 126.2, 126.5, 127.6, 128.0,128.4, 128.7, 130.0, 130.4, 130.8, 131.2, 131.3, 131.9, 132.9, 159.0,191.8.

EXAMPLE XII 2-(9-Anthracene)salicylaldehyde

The tetrahydropyran-protected 2-(9-anthracene) salicylaldehyde ofExample XI (8.4 g, 22 mmol) was dissolved in ethanol (75 mL) and THF(100 mL). To the solution was added pyridinium p-toluenesulfonate (0.28g, 1.1 mmol), and the reaction was stirred at reflux overnight. Thesolvents were removed in vacuo to yield 6.7 g (99%) of crude product. HNMR (CDCl₃): 7.25-8.55 (m, 13H), 10.05 (s, 1H), 11.22 (s, 1H); ¹³C NMR(C₆D₆): 120.0, 120.9, 125.3, 125.9, 126.1, 127.3, 127.6, 128.8, 130.3,130.8, 131.5, 134.0, 140.4, 159.9, 196.9.

EXAMPLE XIII HO-3-(9-Anthracene)C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂

2-(Anthracene)salicylaldehyde (6.5 g, 22 mmol), 2,6-diisopropylaniline(4.6 g, 26 mmol), and p-toluenesulfonic acid (215 mg, 1.1 mmol) weredissolved in benzene (250 mL) and stirred under reflux for 3 hours in aDean-Stark apparatus. After this time, the solvent was removed in vacuo,and the resulting residue was washed with hexane (100 mL) and methanol(20 mL), and dried in vacuo. The yield of product was 8.8 g (88%). ¹HNMR (CDCl₃): δ 1.23 (d, 12H, J_(HH)=6.90 Hz), 3.09 (septet, 2H,J_(HH)=6.90 Hz), 7.23-8.52 (m, 15H), 8.59 (s, 1H), 13.33 (s, 1H); ¹³CNMR (C₆D₆): δ 23.8, 28.2, 119.0, 119.1, 123.4, 125.2, 125.6, 125.7,126.7, 127.0, 127.3, 128.5, 128.8, 130.5, 131.6, 132.4, 132.5, 136.8,138.9, 146.3, 159.6, 166.8.

EXAMPLE XIV[O-3-(9-Phenanthrene)C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂]nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product of ExampleIX (0.87 g, 1.6 mmol) and bis(triphenylphosphine)nickel(phenyl)chloride(1.0 g, 1.40 mmol) in benzene (20 mL). The reaction of was stirred atroom temperature for 1.5 hours. After this time, the reaction wasfiltered by cannula filtration, and the filtrate was concentrated invacuo to ˜5 mL. Pentane (30 mL) was added with vigorous stirring. Ayellow-orange solid precipitated from solution, and was isolated bycannula filtration to yield 0.92 g (75%) of a yellow-orange solid. ¹HNMR (C₆D₆): δ 1.08 (d, 6H, J_(HH)=6.96 Hz), 1.19 (d, 6H, J_(HH)=6.96Hz), 1.21 (d, 6H, J_(HH)=6.96 Hz), 1.32 (d, 6H, J_(HH)=6.96 Hz), 4.16(septet, 2H, J_(HH)=6.96 Hz), 6.14-8.37 (m, 35H), 8.13 (d, 1H,J_(HP)=11.36 Hz); ¹³C NMR (C₆D₆): δ 22.6, 25.6, 28.9, 114.2, 119.9,121.2, 122.8, 124.5, 124.7, 124.9, 125.6, 126.1, 127.2, 127.4, 128.4,128.9, 130.5, 130.8, 131.1, 131.5, 131.8, 133.5 (d, J_(CP)=13.4 Hz),134.7, 136.6, 137.4, 138.3, 140.7, 145.2, 146.4, 150.1, 165.2, 166.7;³¹P NMR (C₆D₆): δ 25.09. Anal. Calcd for C₅₇H₅₀NNiOP: C, 80.29; H, 5.91;N, 1.64. Found: C, 80.06; H, 6.14; N, 1.25.

EXAMPLE XV[O-3-(9-Anthracene)C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂]nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product of ExampleXIII (0.53 g, 1.6 mmol) andbis(triphenylphosphine)nickel(phenyl)chloride (2.0 g, 2.9 mmol) inbenzene (20 mL). The reaction was stirred at room temperature for 1.5hours. After this time, the reaction was filtered by cannula filtration,and the filtrate was concentrated in vacuo to ˜5 mL. Pentane (30 mL) wasadded with vigorous stirring and the reaction was cooled to −78° C. Ayellow-orange solid precipitated from solution, and was isolated bycannula filtration to yield 0.71 mg (78%) of a yellow-orange solid. ¹HNMR (C₆D₆): δ 1.14 (d, 6H, J_(HH)=6.56 Hz), 1.18 (d, 6H, J_(HH)=6.56Hz), 4.16 (septet, 2H, J_(HH)=6.56 Hz), 6.17-7.83 (m, 40H), 8.15 (d, 1H,J_(HP)=11.32 Hz); ¹³C NMR (C₆D₆): δ 22.6, 25.6, 28.9, 114.2, 119.9,121.2, 122.8, 124.5, 124.7, 124.9, 125.6, 126.1, 127.2, 127.4, 128.4,128.9, 130.5, 130.8, 131.1, 131.5, 131.8, 133.5 (d, J_(CP)=13.4 Hz),134.7, 136.6, 137.4, 138.3, 140.7, 145.2, 146.4, 150.1, 165.2, 166.7;³¹P NMR (C₆D₆): δ 22.99. Anal. Calcd for C₅₇H₅₀NNiOP: C, 80.29; H, 5.91;N, 1.64. Found: C, 79.77; H, 6.09; N, 1.49.

EXAMPLE XVI 2,3-Dihydroxy, 1-(2,6-Diisopropyl)benzaldimine

In a round-bottom flask was dissolved 10 g (72 mmol) of1,2-dihydroxybenzaldehyde, 2,6-diisopropylaniline (16 g, 90 mmol), andformic acid (1 mL) in methanol (20 mL). The solution was stirredvigorously for 5 minutes at which time the light yellow-brown solutionbecame dark red, and a light orange-red solid precipitated fromsolution. The solid was collected by filtration through a glass frit,washed twice with cold methanol (−20° C.), and dried under vacuum toyield 22 g (98%). ¹H NMR (CD₂Cl₂): δ 1.27 (d, 12H, J_(HH)=6.72 Hz), 3.11(septet, 2H, J_(HH)=6.72 Hz), 6.93 (t, 6H, J_(HH)=7.92 Hz), 7.04 (d, 1H,J_(HH)=7.92 Hz), 7.15 (d, 1H, J_(HH)=11.0 Hz) 7.29 (br s, 3H), 8.40 (s,1H); ¹³C NMR (CD₂Cl₂): δ 23.5, 28.4, 118.1, 118.3, 119.1, 123.2, 123.4,126.0, 139.2, 145.4, 145.6, 149.7, 145.6, 167.1.

EXAMPLE XVII HO-3-[O-Si(^(i)PR)₃]C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂

In a Schlenk flask under an atmosphere of N₂ was dissolved the compoundof Example XVI (3.0 g, 10 mmol), triisopropylsilylchloride (2.3 g, 12mmol), and imidazole (0.96 g, 14 mmol) in DMF (40 mL). The reaction wasstirred at room temperature for 4 hours. After this time, Et₂O (250 mL)was added, and the solution was washed twice with water (2×100 mL). TheEt₂O layer was dried with Na₂SO₄ and concentrated on a rotary evaporatorto a yellow-orange oil. The oil was loaded onto a silica gel column andeluted with 95:5 hexane:ethyl acetate. Removal of solvent yielded 4.1 g(89%) of an orange oil. ¹H NMR (C₆D₆): δ 0.99 (d, 12H, J_(HH)=6.86 Hz),1.15 (d, 18H, J_(HH)=6.83 Hz), 1.29 (septet, 3H, J_(HH)=6.83 Hz), 2.93(septet, 2H, J_(HH)=6.86 Hz), 6.59-7.11 (m, 6H), 7.89 (s, 1H), 13.44 (s,1H); ¹³C NMR (C₆D₆): δ 20.4, 23.5, 26.7, 28.4, 118.5, 119.8, 123.5,123.8, 124.9, 125.8, 130.1, 133.4, 135.9, 138.8, 144.8, 153.5, 167.4.

EXAMPLE XVIII HO-3-[O—Si(Ph)₂(t-But)]C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂

In a Schlenk flask under an N₂ atmosphere was dissolved the compound ofExample XVI (3.0 g, 10 mmol), diphenyl-t-butylsilylchloride (3.3 g, 12mmol), and imidazole (0.96 g, 14 mmol) in DMF (40 mL). The reaction wasstirred at room temperature for 4 hours. After this time, Et₂O (250 mL)was added and the solution was washed twice with distilled water (2×100mL). The Et₂O layer was dried with Na₂SO₄ and concentrated on a rotaryevaporator to a yellow-orange oil. The oil was loaded onto a silica gelcolumn and eluted with 90:10 hexane:ethyl acetate. Removal of solventyielded 4.4 g (83%) of an orange oil. ¹H NMR (C₆D₆): δ 0.98 (d, 12H,J_(HH)=6.84 Hz), 1.26 (s, 9H), 2.90 (septet, 2H, J_(HH)=6.84 Hz), 6.28(t, 1H, J_(HH)=7.77 Hz), 6.47 (d, 1H, J_(HH)=7.77 Hz), 6.82 (d, 1H,J_(HH)=7.92 Hz), 7.10 (m, 3H), 7.87 (m, 1H), 13.49 (s, 1H); ¹³C NMR(C₆D₆): δ 13.3, 18.2, 23.4, 28.5, 118.8, 119.8, 123.5, 124.1, 124.9,125.8, 138.8, 145.4, 146.9, 153.7, 167.4.

EXAMPLE XIX[O-3-[O—Si(^(i)Pr)₃]C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product of ExampleXVII (0.70 g, 1.3 mmol) andbis(triphenylphosphine)nickel(phenyl)chloride (1.0 g, 1.4 mmol) inbenzene (30 mL). The reaction of was stirred at room temperature for 30minutes. After this time, the reaction was filtered by cannulafiltration, and the filtrate was concentrated in vacuo to 5 mL. Pentane(30 mL) was added and the reaction was cooled to −78° C. and stored atthis temperature for 2 days. A yellow-orange solid precipitated fromsolution, and was isolated by cannula filtration to yield 0.70 g (57%)of a waxy, yellow-orange solid. ¹H NMR (C₆D₆): δ 0.84 (br s, 18H), 1.09(d, 6H, J_(HH)=7.32 Hz), 1.21 (d, 6H, J_(HH)=7.32 Hz), 4.20 (septet, 2H,J_(HH)=7.32 Hz), 6.15-7.80 (m, 30H), 7.97 (d, 1H, J_(HP)=8.72 Hz); ¹³CNMR (C₆D₆): δ 13.0, 18.0, 22.8, 25.5, 28.9, 113.1, 120.4, 120.7, 121.0,122.7, 125.0, 125.9, 126.2, 129.5, 132.4, 132.8, 134.1, 134.8 (d,J_(CP)=9.76 Hz), 136.7, 138.0, 140.7, 149.2, 150.0, 159.0, 166.0; ³¹PNMR (C₆D₆): δ 23.13.

EXAMPLE XX[O-3-[O—Si(Ph)₂(t-Bu)]C₆H₃-o-C(H)—N═C-2,6-C₆H₃(i-Pr)₂Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the compound of ExampleXVIII (0.81 g, 1.3 mmol) andbis(triphenylphosphine)nickel(phenyl)chloride (1.0 g, 1.4 mmol) inbenzene (30 mL). The reaction was stirred at room temperature for 1.5hours. After this time, the reaction was filtered by cannula filtration,and the filtrate was concentrated in vacuo to ˜5 mL. Pentane (30 mL) wasadded with vigorous stirring, and the reaction was cooled to −25° C. Ayellow-orange solid precipitated from solution, and was isolated bycannula filtration to yield 0.92 g (68%) of a yellow-orange solid. ¹HNMR (C₆D₆): δ 0.52 (s, 9H), 1.05 (d, 6H, J_(HH)=6.60 Hz), 1.21 (d, 6H,J_(HH)=6.60 Hz), 4.12 (septet, 2H, J_(HH)=6.60 Hz), 6.18-7.75 (m, 40H),7.94 (d, 1H, J_(HP)=9.16 Hz); ¹³C NMR (C₆D₆): δ 18.8, 22.7, 25.5, 26.3,28.8, 99.8, 113.1, 120.5, 121.1, 122.5, 122.9, 125.0, 126.2, 127.5,129.6, 130.0, 132.5, 133.6, 134.9 (d, J_(CP)=9.76 Hz), 135.7, 136.7,140.8, 148.6, 150.0, 155.6, 158.8, 159.1, 166.2; ³¹P NMR (C₆D₆): δ22.78. Anal. Calcd for C₅₉H₆₀NNiO₂PSi: C, 75.96; H, 6.48; N, 1.50;Found: C, 75.57; H, 6.74; N, 1.03.

EXAMPLE XXI[(4S)-4,5-Dihydro-2-(2′-oxidophenyl-χO)-4-isopropyloxazole-χN)]nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of(4S)-4,5-dihydro-2-(2′-hydroxyphenyl)-4-isopropyloxazole (470 g, 1.6mmol) and bis(triphenylphosphine)nickel(phenyl)chloride (1.0 g, 1.4mmol) in benzene (20 mL). The reaction was stirred at room temperaturefor 1.5 hours. After this time, the reaction was filtered by cannulafiltration, and the filtrate was concentrated in vacuo to ˜3 mL. Pentane(30 mL) was added with vigorous stirring and the reaction was cooled to−78° C. A yellow-orange solid precipitated from solution, and wasisolated by cannula filtration to yield 0.54 g (62%) of a yellow-orangesolid. ¹H NMR (C₆D₆): δ 0.24 (d, 3H, J_(HH)=8.80 Hz), 0.63 (d, 3H,J_(HH)=8.80 Hz), 2.24 (septet, 1H, J_(HH)=8.80 Hz), 2.92 (d of d, 1H,J_(HH)=8.32 Hz, J_(HH′)=2.92 Hz), 3.36 (t, 1H, J_(HH)=8.80 Hz), 3.64 (dof d, 1H, J_(HH)=8.32 Hz, J_(HH′)=2.92 Hz), 6.09-7.73 (m, 29H); ¹³C NMR(C₆D₆): δ 68.0, 74.2, 109.3, 113.1, 121.6, 122.5, 122.6, 126.3, 127.4,127.8, 127.9, 128.3, 128.6, 129.6, 131.1, 131.5, 133.5, 133.7, 133.9,134.5 (d, J_(CP)=10.4 Hz), 143.4, 149.1, 149.5, 166.5, 168.8; ³¹P NMR(C₆D₆): δ 28.88.

EXAMPLE XXII[(4S)-4,5-Dihydro-2-(2′oxidophenyl-χO)-4-isopropyloxazole-χN)]nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of(4S)-4,5-dihydro-2-(2′-hydroxyphenyl)-4-isopropyloxazole (530 g, 1.6mmol) and bis(triphenylphosphine)nickel(phenyl)chloride (1.0 g, 1.4mmol) in benzene (20 mL). The reaction was stirred at room temperaturefor 1.5 hours. After this time, the reaction was filtered by cannulafiltration, and the filtrate was concentrated in vacuo to ˜5 mL. Pentane(30 mL) was added with vigorous stirring, and the reaction was cooled to−78° C. A yellow-orange solid precipitated from solution, and wasisolated by cannula filtration to yield 0.71 g (78%) of a yellow-orangesolid. ¹H NMR (C₆D₆): δ 4.13 (d of d, 1H, J_(HH)=8.32 Hz, J_(HH′)=8.32Hz), 4.22 (d of d, 1H, J_(HH)=8.32 Hz, J_(HH′)=8.32 Hz), 4.43 (t, 1H,J_(HH)=8.32 Hz), 6.09-7.73 (m, 29H); ¹³C NMR (C₆D₆): δ 68.0, 74.2,109.3, 113.1, 121.6, 122.5, 122.6, 126.3, 127.4, 127.8, 127.9, 128.3,128.6, 129.6, 131.1, 131.5, 133.5, 133.7, 133.9, 134.5 (d, J_(CP)=10.4Hz), 143.4, 149.1, 149.5, 166.5, 168.8; ³¹P NMR (C₆D₆): δ 28.01. Anal.Calcd for C₃₉H₃₂NNiO₂P: C, 73.61; H, 5.07; N, 2.20. Found: C, 73.77; H,5.24; N, 2.23.

EXAMPLE XXIII HO-5-(OMe)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a methanol (25 mL) solution of 4-methoxysalicylaldehyde (10 g, 66mmol) was added formic acid (1.0 mL) and 2,6-diisopropylaniline (15 g,65 mmol). The resulting mixture was stirred at room temperature for 1hour. After this time, the solution was stored at −25° C. for 24 hours.Yellow crystals precipitated from solution. The crystals were filteredand washed with −25° C. methanol (2×20 mL) to yield 15 g (72%) of ayellow solid. ¹H NMR (C₆D₆): δ 1.07 (d, 12H, J_(HH)=8.56 Hz), 2.98(septet, 2H, J_(HH)=8.56 Hz), 3.29 (s, 3H), 6.60-7.16 (m, 6H), 7.86 (s,1H), 12.89 (s, 1H); ¹³C NMR (C₆D₆): δ 23.5, 28.5, 55.3, 115.8, 118.7,120.7, 123.5., 125.8, 138.7, 147.1, 152.7, 156.2, 167.

EXAMPLE XXIV HO-5-(NO₂)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a methanol (15 mL) solution of 4-nitrosalicylaldehyde (10 g, 60 mmol)was added formic acid (1.0 mL) and 2,6-diisopropylaniline (13 g, 75mmol). The resulting mixture was stirred at room temperature for 10minutes. After this time, yellow crystals precipitated from thesolution. The crystals were filtered and washed with methanol (2×20 mL)to yield 15 g (96%) of a yellow solid. ¹H NMR (CD₂Cl₂): δ 1.19 (d, 12H,J_(HH)=6.85 Hz), 2.96 (septet, 2H, J_(HH)=6.85 Hz), 7.14 (d, 1H,J_(HH)=9.18 Hz), 7.23 (br s, 3H), 8.30 (d, 1H, J_(HH)=9.18 Hz), 8.40 (s,1H), 8.43 (s, 1H), 14.30 (s, 1H); ¹³C NMR (CD₂Cl₂): δ 23.6, 28.6, 118.6,123.8, 126.6, 128.7, 128.8, 133.1, 139.1, 140.9, 145.2, 166.0, 167.4.

EXAMPLE XXV HO-3,5-Cl₂C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a methanol (15 mL) solution of 4,6-dichlorosalicylaldehyde (10 g, 52mmol) was added formic acid (1.0 mL) and 2,6-diisopropylaniline (12 g,65 mmol). The resulting mixture was stirred at room temperature for 10minutes. After this time, yellow crystals precipitated from thesolution. The crystals were filtered and washed with methanol (2×20 mL)to yield 17 g (95%) of a yellow solid. ¹H NMR (C₆D₆): δ 0.98 (d, 12H,J_(HH)=6.88 Hz), 2.77 (septet, 2H, J_(HH)=6.88 Hz), 6.60-7.11 (m, 5H),7.47 (s, 1H), 14.02 (s, 1H); ¹³C NMR (C₆D₆): δ 23.2, 28.2, 119.6, 123.1,123.2, 123.3, 126.2, 129.7, 132.9, 138.3, 145.4, 156.3, 165.5.

EXAMPLE XXVI[O-5-(OMe)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product from ExampleXXII (0.64 g, 1.6 mmol) andbis(triphenylphosphine)nickel(phenyl)chloride (1.0 g, 1.4 mmol) inbenzene (20 mL). The reaction was stirred at room temperature for 1hour. After this time, the reaction was filtered by cannula filtration,and the filtrate was concentrated in vacuo to ˜5 mL. Pentane (30 mL) wasadded to the vigorously stirred solution, which was then cooled to −78°C. A yellow-orange solid precipitated from solution, and was isolated bycannula filtration to yield 0.88 g (86%) of a yellow-orange solid. ¹HNMR (C₆D₆): δ 1.08 (d, 6H, J_(HH)=6.84 Hz), 1.30 (d, 6H, J_(HH)=6.84Hz), 3.31 (s, 3H), 4.09 (septet, 2H, J_(HH)=6.84 Hz), 3.29 (s, 3H),6.32-7.69 (m, 40H), 7.88 (d, 1H, J_(HP)=9.28 Hz); ¹³C NMR (C₆D₆): δ22.6, 25.6, 28.8, 55.4, 113.1, 117.6, 121.2, 122.6, 123.7, 125.0, 125.2,126.0, 129.4, 131.6, 132.0, 134.5 (d, J_(CP)=9.76 Hz), 138.2, 140.6,149.4, 150.4, 161.9, 165.7; ³¹P NMR (C₆D₆): δ 24.63, Anal. Calcd forC₄₄H₄₄NNiO₂P: C, 74.59; H, 6.26; N, 1.98. Found: C, 74.01; H, 6.20; N,1.65.

EXAMPLE XXVII[O-5-(NO₂)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the compound of ExampleXXIV (0.56 g, 1.6 mmol) andbis(triphenylphosphine)nickel(phenyl)chloride (1.0 g, 1.4 mmol) inbenzene (20 mL). The reaction was stirred at reflux for 1 hour. Afterthis time, the reaction was filtered by cannula filtration, and thefiltrate was concentrated in vacuo to ˜5 mL. Pentane (30 mL) was addedto the vigorously stirred solution. A light-green solid precipitatedfrom solution, and was isolated by cannula filtration to yield 0.84 g(89%) of a yellow-orange solid. ¹H NMR (C₆D₆): δ 0.96 (d, 6H,J_(HH)=6.96 Hz), 1.22 (d, 6H, J_(HH)=6.96 Hz), 3.89 (septet, 2H,J_(HH)=6.96 Hz), 5.91-7.90 (m, 30H), 8.06 (d, 1H, J_(HP)=2.92 Hz); ¹³CNMR (C₆D₆): δ 22.2, 25.5, 28.7, 118.4, 121.4, 122.4, 122.6, 123.3,125.2, 126.1, 128.0, 128.3, 129.9, 130.4, 130.9, 131.7, 134.2 (d,J_(CP)=9.91 Hz), 137.5, 140.1, 149.0, 165.8, 170.5; ¹³P NMR (C₆D₆): δ25.51.

EXAMPLE XXVIII[O-3,5-Cl₂C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the compound of exampleXXV (0.66 g, 1.5 mmol) and bis(triphenylphosphine)nickel(phenyl)chloride(1.0 g, 1.4 mmol) in benzene (20 mL). The reaction was stirred at roomtemperature for 1 hour. After this time, the reaction was filtered bycannula filtration, and the filtrate was concentrated in vacuo to ˜5 mL.Pentane (30 mL) was added to the reaction. A yellow-orange solidprecipitated from solution, and was isolated by cannula filtration toyield 0.91 g (74%) of a yellow-orange solid. ¹H NMR (C₆D₆): δ 0.98 (d,6H, J_(HH)=6.80 Hz), 1.22 (d, 6H, J_(HH)=6.80 Hz), 3.92 (septet, 2H,J_(HH)=6.80 Hz), 6.25-7.67 (m, 30H); ¹³C NMR (C₆D₆): δ 22.6, 25.5, 28.8,117.4, 120.0, 122.8, 125.3, 126.2, 128.3, 128.6, 129.7, 130.5, 131.0,131.5, 133.3, 133.8, 134.0, 134.4 (d, J_(CP)=9.77 Hz), 137.4, 140.1,149.4, 159.6, 165.2; ³¹P NMR (C₆D₆): δ 25.93. Anal. Calcd forC₄₃H₄₀Cl₂NNiOP: C, 69.29; H, 5.41; N, 1.88. Found: C, 69.87; H, 5.74; N,1.63.

EXAMPLE XXIX p-Trifluoromethylsalicylaldehyde

To a solution of p-trifluoromethylphenol (7.1 g, 44 mmol) and2,6-lutidine (1.9 g, 17.6 mmol) in toluene (80 mL) was slowly addedSnCl₄ (1.2 g, 4.4 mmol). The solution was stirred at room temperaturefor 20 minutes. Paraformaldehyde was added (3.2 g, 106 mmol) and thereaction was stirred at 110° C. for 12 hours. After cooling to roomtemperature, the reaction mixture was poured into water (250 mL), andadjusted to pH 1 with concentrated HCl. The mixture was extracted withdiethyl ether (500 mL), and the organic layer was washed twice withsaturated brine and dried over Na₂SO₄. The solvent was removed by rotaryevaporation to leave a yellow oil. The oil was loaded onto a silica gelcolumn and eluted with 6:1 hexane:ethyl acetate. The yield of productwas 1.0 g (12%). ¹H NMR (CDCl₃): δ 7.21-7.91 (m, 12H), 9.91 (s, 1H),11.32 (s, 1H).

EXAMPLE XXX HO-5-(CF₃)C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a methanol (10 mL) solution of 5-trifluoromethylsalicylaldehyde (0.7g, 4.1 mmol) was added formic acid (0.5 mL) and 2,6-diisopropylaniline(0.8 g, 4.5 mmol). The resulting mixture was stirred at room temperaturefor 15 minutes. After this time, it was kept at −80° C. for 1 hour,yellow crystals precipitated from the solution. The crystals werefiltered, dried under vacuum to yield 1.2 g (85%) of a yellow solid. ¹HNMR (C₆D₆): δ 1.04 (d, 12H), 2.85 (septet, 2H, J=6.88 Hz), 6.85-7.25 (m,5H), 7.61 (s, 1H), 13.82 (s, 1H).

EXAMPLE XXXI[O-5-(CF₃)C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of Example XXX (0.4 g, 0.6mmol) and bis(triphenylphosphine)nickel(phenyl)chloride 0.46 g, 0.6mmol) in benzene (15 mL). The reaction was stirred at room temperaturefor 1 hour. After this time, the reaction was filtered by cannulafiltration, and the filtrate was concentrated in vacuo to ˜2 mL. Pentane(20 mL) was added to the vigorously stirred solution, which was thencooled to −78° C. A yellow-orange solid precipitated from solution, andwas isolated by cannula filtration to yield 0.6 g (65%) of ayellow-orange solid. ¹H NMR (C₆D₆): δ 0.95 (d, 6II, J_(HH)=6.84 Hz),1.20 (d, 6H, J_(HH)=6.84 Hz), 3.95 (septet, 2H, J_(HH)=6.84 Hz),6.32-7.81 (m, 40H, 31p NMR (C₆D₆): δ 26.10.

EXAMPLE XXXII HO-3,5-(NO₂)₂C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

3,5-dinitrosalicylaldehyde was converted to the correspondingsalicylaldimine by reaction with 2,6-diisopropylaniline according to thegeneral procedure of Example XXIV. The yield of the3,5-dinitrosalicylaldimine compound was 70%.

EXAMPLE XXXIII[O-3,5-(NO₂)₂C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

The product of Example XXXII was reacted withbis(triphenylphosphine)nickel(phenyl)chloride according to the generalprocedure of Example XXVII. The yield of the 3,5-dinitrosalicylaldiminenickel (II) complex was 58%.

EXAMPLE XXXIV General Procedure for Nitration of 3-R¹-Salicylaldehydes

To a solution of 5 mmol of the 3-R¹-salicylaldehyde in 10 ml of glacialacetic acid is added at room temperature 1 or 2 equivalents ofconcentrated HNO₃. After stirring for 40 minutes at room temperature,the mixture is poured into 100 ml of water. The yellow precipitate iscollected by vacuum filtration, washed with water and dried in vacuo.

Using this procedure, the following 3-R¹-salicylaldehydes were nitrated(yield of nitration product in parentheses): 6-t-butylsalicylaldehyde(82%), 6-phenylsalicylaldehyde (71%), and2-(9-anthracene)salicylaldehyde from Example XII (88% for mono-nitrationat the 10-position of anthracene, 64% for di-nitration at the 10position of the anthracene and para-position of the salicylaldehydering).

EXAMPLE XXXV HO-(3-t-Bu)(5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

The nitrated product of t-butylsalicylaldehyde prepared according to thegeneral procedure of Example XXXIV was converted to the imine bycondensation with 2,6-diisopropylaniline using a procedure analogous toExample III. The yield of the imine derivative was 63%.

EXAMPLE XXXVI[O-(3-t-Bu)(5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

The Na salt of the product from Example XXXV was reacted withbis(triphenylphosphine)nickel(phenyl)chloride according to a procedureanalogous to Example V. The yield of the salicylaldimine nickel (II)complex was 40%.

EXAMPLE XXXVII HO-(3-Ph)(5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

The nitrated product of 6-phenylsalicylaldehyde prepared according tothe general procedure of Example XXXIV was converted to thecorresponding imine by condensation with 2,6-diisopropylaniline using aprocedure analogous to Example IV. The yield of the imine derivative was83%.

EXAMPLE XXXVIII[O-(3-Ph)(5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

The Na salt of the product from Example XXXVII was reacted withbis(triphenylphosphine)nickel(phenyl)chloride according to a procedureanalogous to Example VI. The yield of the salicylaldimine nickel (II)complex was 77%.

EXAMPLE XXXVIXOH-3-[9-(10-NO₂-Anthracene)](5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

The di-nitrated product of 2-(anthracene) salicylaldehyde (see ExampleXII for synthesis of this aldehyde), prepared according to the generalprocedure of Example XXXIV, was converted to the corresponding imine bycondensation with 2,6-diisopropylaniline using a procedure analogous toExample XIII. The yield of the imine derivative was 66%.

EXAMPLE XL{O-3-[9-(10-NO₂-Anthracene)](5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₃(i-Pr)₂}nickel(phenyl)(PPh₃)

The Na salt of the product from Example XXXVIX was reacted withbis(triphenylphosphine)nickel(phenyl)chloride according to a procedureanalogous to Example XIV. The yield of the salicylaldimine nickel (II)complex was 72%.

EXAMPLE XLI HO-3-[9-(10-NO₂-Anthracene)]C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

The mono-nitrated product of 2-(anthracene) salicylaldehyde (see ExampleXII for synthesis of this aldehyde), prepared according to the generalprocedure of Example XXXII, was converted to the corresponding imine bycondensation with 2,6-diisopropylaniline using a procedure analogous toExample IX. The yield of the imine derivative was 70%.

EXAMPLE XLII{O-3-[9-(10-NO₂-Anthracene)]C₆H₃-o-C(H)═N-2,6-C₆H₃(i-Pr)₂}nickel(phenyl)(PPh₃)

The Na salt of the product from Example XLI was reacted withbis(triphenylphosphine)nickel(phenyl)chloride according to a procedureanalogous to Example XIV. The yield of the salicylaldimine nickel (II)complex was 70%.

EXAMPLE XLIII HOC₁₀H₆-o-C(H)═N-2,6-C₆H₃(i-Pr)₂

To a solution of 5.75 of 2-hydroxynaphthaldehyde and 7.6 mL of2,6-diisopropylaniline in 100 mL of benzene was added 0.32 g ofp-toluenesulfonic acid. The mixture was heated at reflux using aDean-Stark trap for 16 hours. After cooling to room temperature, thesolvent is evaporated on a rotary evaporator. Upon addition of 30 mL ofmethanol to the residue, an orange precipitate was formed. Theprecipitate was filtered and dried in vacuo. The yield of orange solidwas 85%.

EXAMPLE XLIV [OC₁₀H₆-o-C(H)═N-2,6-C₆H₃(i-Pr)₂]Nickel(phenyl)(PPh₃)

The Na salt of the product of Example XLIII was prepared by reaction ofthe product of Example XLIII (2.0 g) in 60 mL of THF with 0.30 g of NaH.The mixture was stirred for 1 hour at room temperature. After filtrationof the reaction solution through a frit filter containing Celite, thesolvent was evaporated. The yield of Na salt was 97%.

To a mixture of 0.49 g of the Na salt of the product of Example XLIIIand 0.96 g of bis(triphenylphosphine)nickel(phenyl)chloride was added atroom temperature 30 mL of benzene. After stirring at room temperaturefor 5 hours, the mixture was filtered (frit with Celite) and the volumeof the dark red solution was reduced in vacuo to ˜3 mL. Pentane (30 mL)was added and the mixture was cooled to −50° C. An orange precipitatewas formed. The precipitate was filtered and dried in vacuo. The yieldof orange solid was 75%.

EXAMPLE XLV

Some of the above late transition metal salicylaldimine late transitionmetal chelates were used in the catalytic polymerization of ethyleneaccording to the following general procedure: The catalyst, in amountsindicated in the below table, was weighed and placed into a pressurecontainer under an atmosphere of nitrogen. The pressure container wasthen evacuated and backfilled with ethylene. 80 mL of dry toluene wasthen cannula transferred into the pressure container followed byaddition of 5 mL of a toluene solution containing the phosphine spongeadjunct, bis(cyclooctadienenickel[Ni(COD)₂] ortris(pentafluorophenyl)boron[(B(C₆F₅)₃]. The ethylene pressure wasraised to that indicated in Table 1 below and maintained at theprescribed pressure. The indicated temperature was the initialtemperature of the reactor. In all reactions (except those run at 0° C.)the temperature was allowed to rise due to the reaction exotherm. Thereaction was run with stirring for forty minutes. The polymerizationprocess was terminated and 500 mL of methanol was added to the toluenesolution to precipitate the polyethylene product. The polyethylene wascollected by filtering the material through a glass frit filter. Thenumber of branches of C₁+C₂+C₃+C₄ and higher of the polymer wasestimated using ¹³C NMR analysis of the resultant polymer in hot1,3,5-trichlorobenzene. Polymer molecular weight was determined by gelpermeation chromatography in trichlorobenzene at 135° C. and is relativeto broad polyethylene calibration standards.

EXAMPLE XLVI OH-3-(9-Anthracene)C₆H₃-o-C(H)═N-2,6-C₆H₂(i-Pr)₂(4-NO₂)

The 3-(anthracene) salicyladehyde was converted to the correspondingimine by condensation with 2,6-diisopropyl-4-nitroaniline using aprocedure analogous to Example XIII. The yield of the imine derivativewas 81%.

EXAMPLE XLVII(O-3-(9-Anthracene)C₆H₃-o-C(H)═N-2,6-C₆H₂(i-Pr)₂(4-NO₂))nickel(phenyl)(PPh₃)

In a Schlenk flask was dissolved the Na salt of the product of ExampleXLVI (1.44 g, 2.15 mmol) andbis(triphenylphosphine)nickel(phenyl)chloride (1.45 g, 2.08 mmol) inbenezene (25 mL). The reaction was stirred at room temperature for 16hours. After this time the reaction was evaporated, the residueextracted with methylene chloride (25 mL), filtered by cannulafiltration, and the filtrate was evaporated. The residue was washed withpentane (25 ml) and dried in vacuum to yield 1.00 g (52%) of an orangesolid.

EXAMPLE XLVIIIOH-3-[9-(10-NO₂-Anthracene)](5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₂(i-Pr)₂(4-NO₂)

The di-nitrated product of 3-(anthracene) salicyladehyde (see ExampleXII for synthesis of this aldehyde), prepared according to the generalprocedure of Example XXXIV, was converted to the corresponding imine bycondensation with 2,6-diisopropyl-4-nitroaniline using a procedureanalogous to Example XIII. The yield of the imine derivative was 50%.

EXAMPLE XLVIX(O-3-[9-(10-NO₂-Anthracene)](5-NO₂)C₆H₂-o-C(H)═N-2,6-C₆H₂(i-Pr)₂(4-NO₂))nickel(phenyl)(PPh₃)

The Na salt of the product of Example XLVIII was reacted withbis(triphenylphosphine)nickel(phenyl)chloride according to a procedureanalogous to Example XLVII. The yield of the salicylaldimine nickel (II)complex was 70%.

TABLE 1 Polymerization of Ethylene Bran- ches Cat. [Cat] Adjuct TempPress Yield Total/ Ex. No. mM equiv. (° C.) (psi) (g) PDI^(a) Mw 1000 II1.8 2¹ 25 80 2.0 1.54 4,000 45 II 1.8 2¹ 25 200 2.4 1.45 10,000 20 V 1.82¹ 25 80 8.0 2.25 26,000 55 VI 1.8 2¹ 25 80 20.0 2.28 23,300 40 V 0.9 2¹25 80 3.5 1.84 11,400 55 VI 0.9 2¹ 25 80 8.9 1.95 11,000 45 V 0.9 2¹ 080 3.1 3.10 6,600 25 VI 0.9 2¹ 0 80 3.9 2.45 108,000 10 V 0.9 2¹ 25 803.5 1.84 18,400 55 V 0.9 8¹ 25 80 4.8 2.34 43,200 40 V 0.9 1² 25 80 4.21.69 10,400 55 V 0.9 2² 25 80 3.3 2.55 11,000 45 XIV^(b) 0.9 2¹ 25 807.0 3.85 37,700 30 XIV^(b) 0.5 2¹ 25 80 0.8 2.30 56,700  5 XIV^(b) 0.92² 25 80 7.0 6.84 49,500 35 XIV^(b) 0.9   0.5² 25 80 5.0 3.63 42,500 20XIV^(b) 0.9 — 25 80 0.4 2.53 14,900 15 XV^(b) 0.9 2¹ 25 80 7.4 6.4354,000  0 XV^(b) 0.9 2² 25 80 5.0 7.19 23,800 50 XXVI^(b) 0.9 2¹ 25 801.0 1.68 7,300 39 II^(b) 0.9 2¹ 25 80 2.0 1.54 4,000 XXVII^(b) 0.9 2¹ 2580 8.0 18.0 143,000 32 XXVIII^(b) 0.9   0.5¹ 25 80 1.5 3.28 22,500  9XXVII^(b) 0.5  1.0 25 80 3.0 18.0 366,000 12 XXXI 1.8 2¹ 25 80 0.9 XXXI0.9 2² 25 80 2.7 XXXIII 1.8 2¹ 25 80 7.7 XXXVI 0.9 2¹ 25 80 3.2 ˜25^(c)XXXVIII 0.9 2¹ 25 80 7.0 ˜13^(c) XL 0.9 2¹ 25 80 6.5 ˜20^(c) XL 0.9 2²25 80 9.7 ˜55^(c) XLII 0.9 2¹ 25 80 4.0 ˜15^(c) XLII 0.9 2¹ 25 80 3.3 ˜5^(c) XLII 0.9 2² 25 80 7.0 ˜22^(c) XLIV 0.5 2² 50 80 2.3 XLIV 0.9 2²25 80 2.3 XLIV 0.9 2¹ 25 80 0.4 ^(a)PDI = Polydispersity index, Mw/Mn^(b)Polymerization run 15 minutes ^(c)Estimated from peak meltingtemperature on DSC scan. ¹Adjunct used was Ni(COD)₂ ²Adjunct used wasB(C₆F₅)₃

EXAMPLE L

A series of polymerizations were carried out using nickel (II)salicylaldimine catalyst of the present invention, alone or, as part ofa catalyst composition, in combination with a co-catalyst adjunct agentB(C₆F₅)₃ and/or a Lewis base. The procedures under which thesepolymerizations were conducted are outlined herein below and thespecifics and results are given in the Tables which follow.

The salicylaldimine catalysts used are of compound I type wherein:

Catalyst “A”: R¹ is 9-anthracenyl; R², X, R³, and R⁴ are each hydrogen;R⁵ is 2,6-diisopropyl phenyl; R⁶ is phenyl; L is triphenyl phosphine; Ais oxygen and M is nickel.

Catalyst “B”: R¹ is phenyl; R², X, R³, and R⁴ are each hydrogen; R⁵ is2,6-diisopropylphenyl; R⁶ is phenyl; L is triphenyl phosphine; A isoxygen and M is nickel.

Catalyst “C”: R¹ is 9-phenanthracenyl; R², X, R³, and R⁴ are eachhydrogen; R⁵ is 2,6-diisopropyl phenyl; R⁶ is phenyl; L is triphenylphosphine; A is oxygen and M is nickel.

Catalyst “D”: R¹ is hydrogen; R², X, R³, and R⁴ are each hydrogen; R⁵ is2,6-diisopropylphenyl; R⁶ is phenyl; L is triphenyl phosphine; A isoxygen and M is nickel.

Catalyst “E”: R¹ is 9-phenanthracenyl; R², R³ and R⁴ are each hydrogen;X is nitro; R⁵ is 2,6-diisopropylphenyl; R⁶ is phenyl; L is triphenylphosphine; A is oxygen and M is nickel.

Catalyst “F”: R¹ is phenyl; R², R³ and R⁴ are each hydrogen; X is nitro;R⁵ is 2,6-diisopropylphenyl; R⁶ is phenyl; L is triphenyl phosphine; Ais oxygen and M is nickel.

Catalyst “G”: R¹ is 10-nitroanthracenyl; R², R³ and R⁴ are eachhydrogen; R⁵ is 2,6-diisopropylphenyl; R⁶ is phenyl; L is triphenylphosphine; A is oxygen and M is nickel.

Catalyst “H”: R¹ is 10-nitroanthracenyl; R², R³, and R⁴ are eachhydrogen; R⁵ is 2,6-diisopropyl 4-nitrophenyl; X is nitro; R⁶ is phenyl;L is triphenyl phosphine; A is oxygen and M is nickel.

Catalyst “I”: R¹ is anthracenyl; R², R³ and R⁴ are each hydrogen; R⁵ is2,6-diisopropyl-4nitrophenyl; R⁶ is phenyl; L is triphenyl phosphine; Ais oxygen and M is nickel.

Catalyst “J”: R¹ is 10-nitroanthracenyl; R², R³ and R⁴ are eachhydrogen; X is nitro; R⁵ is 2,6-diisopropylphenyl; R⁶ is phenyl; L istriphenyl phosphine; A is oxygen and M is nickel.

(1) Polymerization with Catalyst Composition Containing Catalyst ofCompound I with B(C₆F₅)₃ as Co-catalyst adjunct and diethyl ether asLewis base additive.

The appropriate amount of Ni complex and co-catalyst adjunct wereweighed into a 6 oz glass pressure bottle under an atmosphere of N₂. Thesolvent (generally 90 mL dry toluene) was then cannula transferred intothe pressure bottle under a positive pressure of ethylene, followed bythe specified amount of diethyl ether. The ethylene pressure was raisedand maintained between 85 and 100 psig. When specified, temperaturecontrol was accomplished by a water bath to control the exotherm.Stirring of the reaction mixture was maintained by a magnetic stirrerand stir bar. After completion of the polymerization reaction, methanol(1000 mL) and 1N hydrochloric acid (50 mL) was added to the toluenesolution to precipitate the polymer and remove catalyst residue. Thepolyethylene product was collected by filtration through a glass frit,washed with methanol (100 mL) and dried under vacuum.

(2) Polymerization with Catalyst of Compound I Without Co-catalystAdjunct or Lewis Base Additive.

The appropriate amount of Ni complex was weighed into either a 6 or 12oz. glass pressure bottle under an atmosphere of N₂. The solvent (90 mL)was then cannula transferred into the pressure bottle under a positivepressure of ethylene. The ethylene pressure was raised and maintainedbetween 85 and 100 psig. When specified, temperature control wasaccomplished by a water bath to control the exotherm. Stirring of thepolymerization mixture was maintained by a magnetic stirrer and stirbar. In cases where the viscosity of the polymerization mixtureincreased to the point where ethylene consumption slowed significantly,the pressure was released and additional amounts of solvent were added.Subsequently, the mixture was re-pressurized with ethylene. Aftercompletion of the polymerization reaction, methanol (1000 mL) and 1Nhydrochloric acid (50 mL) was added to the toluene solution toprecipitate the polymer and remove catalyst residue. The polyethyleneproduct was collected by filtration through a glass frit, washed withmethanol (100 mL) and dried under vacuum.

(3) Polymerization with Catalyst Composition Composed of Catalyst ofCompound I with Different Lewis Base Additives.

The appropriate amount of Ni complex was weighed into either a 6 or 12oz. glass pressure bottle under an atmosphere of N₂. The solvent (90 mL)was then cannula transferred into the pressure bottle under a positivepressure of ethylene, followed by the specified amount of additive. Theethylene pressure was raised and maintained between 85 and 100 psig.When specified, temperature control was accomplished by a water bath.Stirring of the polymerization mixture was maintained by a magneticstirrer and stir bar. In cases where the viscosity of the polymerizationmixture increased to the point where ethylene consumption slowedsignificantly, the pressure was released and additional amounts ofsolvent were added. Subsequently, the mixture was re-pressurized withethylene. After completion of the polymerization reaction, methanol(1000 mL) and 1N hydrochloric acid (50 mL) was added to the toluenesolution to precipitate the polymer and remove catalyst residue. Thepolyethylene product was collected by filtration through a glass frit,washed with methanol (100 mL) and dried under vacuum.

(4) Polymerizations Carried out at Elevated Ethylene Pressure.

A 1.5 liter Parr stainless steel reactor was charged with theappropriate amount of Ni complex, the specified volume of benzene, anddiethyl ether in a dry box under an atmosphere of N₂. The reactor wasassembled, removed from the dry box, and pressurized with ethylene (500psig unless specified otherwise). The ethylene pressure was maintainedbetween 490 and 500 psig unless specified otherwise. No temperaturecontrol was provided. Stirring of the reaction mixture was maintained bya magnetic stirrer and stir bar. After completion of the polymerizationreaction, methanol (1000 mL) and 1N hydrochloric acid (50 mL) was addedto the benzene solution to precipitate the polymer and remove catalystresidue. The polyethylene product was collected by filtration through aglass frit, washed with methanol (100 mL) and dried under vacuum.

(5) Copolymerizations with Functional Cyclic Olefins.

The appropriate amount of Ni complex was weighed into a 12 oz. FisherPorter pressure bottle under an atmosphere of argon in a dry box. Amechanical stirring assembly and thermocouple was attached, and theapparatus was removed from the dry box. The pressure bottle wasevacuated, then back-filled with ethylene. Dry toluene (100 mL) wascannula transferred into a nitrogen-flushed stainless steel containerfitted with a two-way valve. The container was then pressurized to 50psig (unless specified otherwise) with ethylene. Dry diethyl ether (10or 20 mL) was cannula transferred into another nitrogen-flushedstainless steel container fitted with two-way valve and the containerwas pressurized to 50 psig with ethylene. Into another stainless steelcontainer fitted with two-way valve, a solution of functionalizedmonomer in a small volume of dry toluene was cannula transferred and thecontainer was pressurized with ethylene to 50 psig. In rapid sequentialfashion, the toluene, ether and solution of functionalized monomer, allunder positive ethylene pressure (50 psig), were blown into the FisherPorter bottle. A water bath (40-45° C.) was used to gently warm contentsof the bottle. The bottle was pressurized to 50 psig with ethylene andmaintained at 50 psig over the course of the copolymerization reaction.The reaction typically exothermed to a temperature between 45-55° C.When the uptake of ethylene became negligible, the ethylene pressure wasreleased and the contents of the bottle were poured into 1 liter ofmethanol or acetone. The precipitated polymer was collected by vacuumfiltration, re-suspended in a large volume of methanol, filtered, washedwith fresh methanol and dried under vacuum.

TABLE 2 Polymerization of Ethylene with Catalyst Composition ContainingCocatalyst Adjunct and Lewis Base Additive.^(a) Catalyst Vol. of Et₂OTemperature Productivity Yield PE T_(m) Total Sample (mL) Catalystcontrol (kg PE/mol Ni) (g) M_(w) PDI (° C.) Branches^(b) 1   0.1 A no84.6 5.5 35,600 3.7 120 37 2   0.5 A no 84.6 5.5 32,500 4.2 119 35 3  1A no 92.3 6.0 31,900 4.8 121 42 4  2 A no 107.7 7.0 32,600 5.3 122 47 5 5 A no 104.6 6.8 31,000 5.9 122 51 6 10 A no 130.8 8.5 33,200 5.1 12241 7 20 A no 103.1 6.7 33,000 6.0 125 40 8   90^(c) A no 69.2 4.5 57,0002.8 123 32 9    5^(f) A no 57.5 3.9 78,200 2.0 129 6 10  5 A yes 189.212.3 91,300 3.3 126 22 11  10^(d) A yes 424.6 27.6 172,000 2.7 126 13 12  90^(c,d) A yes 144.6 9.4 106,000 2.4 129 28 13   90^(e) B yes 103 6.815,900 2.2 85 ^(a)All polymerizations reactions were carried out with 55mg of Ni complex and 2 eq. of co-catalyst adjunct, B(C₆F₅)₃ in toluene(90 ml) at 80-90 psig of ethylene. ^(b)Total number of C₁ + C₂ + C₃ + C₄and higher branches per 1000 carbons. ^(c)Diethyl ether used as onlysolvent. ^(d)More solvent added during the reaction. ^(e)THF used asonly solvent. ^(f)Ethyl vinyl ether used.

Table 2 essentially shows the use of Lewis base additive as part ofcatalyst compositions comprising a co-catalyst adjunct, B(C₆F₅)₃, withnickel (II) salicylaldimine catalyst. In total, the data show thatcatalyst productivity and polymer yield increase with increasing amountof diethyl ether. In entries where no temperature control was used,there does not appear to be a significant influence of the ether on thebranching of the polyethylene produced (except ethyl vinyl ether). Ininstances where the polymerization reaction temperature was controlled,the data shows that catalyst productivity and polymer yield is furtherenhanced. Significantly, polymer molecular weight is increased and themolecular weight distribution (PDI) narrows when the temperature iscontrolled. Samples 8, 12 and 13 of Table 2 reveal that the catalyst isactive when ether is present as solvent. Taken together, data in thetable also indicate that the nickel salicylaldimine catalyst performswell with small or even large amounts of a Lewis base compound, such asether.

TABLE 3 Polymerization of Ethylene Without Adjunct or Lewis BaseAdditive^(a) Catalyst Productivity Yield Sam- (kg PE/ PE T_(m) Total pleEntry mol Ni) (g) M_(W) PDI (° C.) Branches^(b)   14^(c) A 842 55.177,300 6.2 120.8 23   15^(c) A 1038 66.7 70,000 5.5 120.1 25 16 E 57537.4 354,000 2.8 136.7 5 17 F 246 16.1 247,000 3.2 131.1 10 18 H 107 6.9177,000 2.4 135.4 5 19 G 776 50.7 238,000 3.6 132.7 8 20 I 938 60.5236,000 2.2 135.5 5 21 J 432 28.2 252,000 2.7 134.0 6 22 B 212 14.1207,000 2.2 132.9 10 23 C 617 40.4 207,000 2.4 129.5 8 ^(a)Allpolymerizations reactions were carried out with 65 μmol of Ni complex intoluene (90 mL initially) at 80-90 psig of ethylenewith temperature control. ^(b)Total number of C₁ + C₂ + C₃ + C₄ andhigher branches per 1000 carbons. ^(c)More solvent added during thereaction.

Table 3 illustrates that nickel (II) salicylaldimine family of catalystsare active polymerization catalysts without any co-catalyst adjunct orLewis base present. This demonstrates that this family of catalyst aretrue single-component polymerization catalysts.

TABLE 4 Polymerization of Ethylene with Catalyst “A” and Diethyl Etheras Additive.^(a) Catalyst Catalyst Vol. of Et₂O Productivity Yield PET_(m) Total Sample loading (mL) (kg PE/mol Ni) (g) M_(w) PDI (° C.)Branches^(b) 24 55 mg 10^(c)  781.8 43.0 165,000 2.2 127 34 25 55 mg10^(c)  923.6 50.8 90,600 7.0 122 25 26 25 mg   5^(c,d) 1220 30.5 62,8005.5 120 28 27 10 mg   5^(c,d) 430.0 4.3 193,000 2.0 132 10 ^(a)Allpolymerizations reactions were carried out in toluene (90 mL) at 80-90psig of ethylene with temperature control. ^(b)Total number of C₁ + C₂ +C₃ + C₄ and higher branches per 1000 carbons. ^(c)More solvent addedduring the reaction. ^(d)Only 50 mL of toluene used at the beginning ofthe reaction.

The significance of Table 4 is that it reveals that the subject catalystis very active in the presence of an oxygenated Lewis base, such asether. In comparison to Table 3 (catalyst A, samples 14 and 15), thecatalyst productivity is shown to be similar. The data for catalyst “A”in Table 4, as compared to catalyst “A” in Table 3, show the benefit ofLewis base to the molecular weight of the polyethylene product. Forcatalyst A, polyethylene of higher molecular weight is generallyproduced when the catalyst composition is comprised of nickel (II)salicylaldimine catalyst and Lewis base.

TABLE 5 Polymerization of Ethylene with Catalyst A and Lewis BaseAdditives.^(a) Catalyst Additive Productivity Yield PE T_(m) TotalSample Additive Amount (kg PE/mol Ni) (g) M_(w) PDI (° C.) Branches^(b)28 THF^(c) 10 mL 467.3 25.7 270,000 2.4 133 5 29 1,4-Dioxane 10 mL 170.99.4 197,000 2.2 137 3 30 Dimethoxyethane^(c) 10 mL 1289 70.9 270,000 2.4136 3 31 Diglyme 10 mL 114.5 6.3 189,000 2.1 136 2 32 Triglyme^(c) 10 mL663.6 36.5 218,000 2.2 134 4 33 Tetraglyme^(c) 10 mL 461.8 25.4 179,0002.4 131 5 34 Anisole 10 mL 45.5 2.5 184,000 2.6 139 4 35 n-Butyl Ether15 mL 58.2 3.2 184,000 2.3 135 4 ^(a)All polymerizations reactions werecarried out with 55 mg of catalyst in toluene (90 mL) at 80-90 psig ofethylene with temperature control. ^(b)Total number of C₁ + C₂ + C₃ + C₄and higher branches per 1000 carbons. ^(c)More toluene added during thereaction.

Table 5 shows that other members of the ether family also are effectiveLewis base additives for the polymerization of ethylene when used withthe subject catalyst. Dimethoxyethane appears to be most effective underthe conditions used, as noted by the highest catalyst productivity andyield of PE. It should be noted that with temperature control, thecatalyst/ether system produces highly linear polyethylene. The polymerproduced is essentially high density polyethylene having a low amount ofbranching and high melting point. Note also that cyclic ethers as wellas linear polyethers are effective additives.

TABLE 6 Polymerization of Ethylene with Catalyst “A” and Various LewisBase Additives.^(a) Catalyst Amount Productivity Yield PE T_(m) TotalSample Additive Additive (kg PE/mol Ni) (g) M_(w) PDI (° C.)Branches^(b) 36 Acetone 10 mL 183.6 10.1 131,000 3.7 128 13 37Ethylacetate 10 mL 121.8 6.7 188,000 2.0 138 38 Ethanol 10 mL 12.7 0.746,600 3.0 129 17 39 Water 0.1 mL 63.6 3.5 90,100 2.0 130 4 40Nitromethane 5 mL 52.7 2.9 140,000 2.4 133 5 41 N,N-Dimethylformamide 10mL 63.6 3.5 140,000 2.4 133 5 42 Phenol 10 g 112.7 6.2 202,000 3.3 134 943 Triethylamine 10 mL 5.5 0.3 28,200 2.6 129 22 ^(a)All polymerizationsreactions were carried out with 55 mg of catalyst in toluene (90 mL) at80-90 psig of ethylene with temperature control. ^(b)Total number ofC₁ + C₂ + C₃ + C₄ and higher branches per 1000 carbons.

Table 6 demonstrates that the subject catalyst is active in the presenceof other Lewis base compounds. Notably, the catalyst remains active andproduces high molecular PE even in the presence of water. Ziegler-Natta,metallocene catalysts and cationic nickel single site catalysts aregenerally not known to tolerate water.

TABLE 7 Polymerization of Ethylene with Various Ni (II) SalicylaldimineCatalysts.^(a) Catalyst Catalyst Amount Productivity Yield PE T_(m)Total Sample Catalyst [mM] Additive Additive (kg PE/mol Ni) (g) M_(w)PDI (° C.) Branches^(b) 44 I 0.71 Et₂O 10 mL 720.0 46.8 197,000 3.5 134 5 45 I 0.71 DME 10 mL 224.6   14.6^(e) 27,600 7.0 118 42 46 I 0.71 DME10 mL 695.4 45.2 208,000 2.3 133  8 47 D 0.94 Et₂O 10 mL 14.5  0.811,400 1.8 95  42^(d) 48 B 0.81 Et₂O 10 mL 85.5  8.2 68,000 4.7 120 2649 F 0.82 Et₂O 10 mL 265.5 14.6 161,000 6.8 128 18 50   J^(c) 0.65Et₂O^(c) 10 mL 469.1 25.8 72,300 5.7 119 19 51 C 0.71 Et₂O^(c) 10 mL472.7 26.0 257,000 2.4 131  5 52 C 0.71 DME^(c)  5 mL 420.0 23.1 85,0003.2 123 16 53   G^(c) 0.60 Et₂O  5 mL 473.7 18.2 315,000 3.6 135.5  6 54  E^(c) 0.73 Et₂O 10 mL 388.4 25.4 194,000 5.9 129.1 12 ^(a)Allpolymerization reactions were carried out in toluene (90 mL) at 80-90psig of ethylene with temperature control. ^(b)Total number of C₁ +C₂ +C₃ + C₄ and higher branches per 1000 carbons. ^(c)More toluene addedduring the reaction. ^(d)Olefinic species detected by NMR. ^(e)Reactionat 45° C.

The data in the above Table 7 indicate that the subject catalysts areactive catalysts for the polymerization of ethylene in the presence ofLewis base.

TABLE 8 Copolymerization of Ethylene and Functionalized Cyclic Olefinswith Catalyst A and Diethyl Ether Additive. Amount Cata- of lyst YieldSam- Com- Com- load- PE ple onomer onomer ing (g) M_(w) % Incorporation48^(a) 5-NAc^(c) 2 mL 100 mg 6.0  3.8 wt % 49^(b) 5-NA1c^(d) 2 g  55 mg1.0 17,200 22.8 wt % ^(a)Polymerization was carried out with 55 mgCatalyst A and 20 ml diethyl ether in toluene (100 mL) at 50 psig ofethylene at 40° C. ^(b)Polymerization was carried out with 55 mgCatalyst A and 10 ml diethyl ether in toluene (90 mL) at 40 psig ofethylene at room temperature. ^(c)5-NAc is 5-norbornen-2-yl acetate.^(d)5-NA1c is 5-norbornen-2-ol.

The data in this Table 8 reveal that the subject catalyst can alsocopolymerize a polar olefinic monomer, such as functionalizednorbornene.

TABLE 9 Comparative Ethylene Polymerizations at Elevated PressureBetween Present Catalyst and Nickel Based Catalyst, SHOP.^(a,b) CatalystTON^(c) Catalyst Concentration Yield PE (kg PE/mol Productivity T_(m)Total Sample Catalyst (mM) (g) cat*hr) (kg PE/mol Ni) M_(w) PDI (° C.)Branches 50 A   0.516^(c) 60 930 546 132,000 18 130.1 19 51 A 0.129 771200 698 65,000 9.4 125.0 28 52 A 0.064 64 660 1156  73,800 6.4 122.6 2853 A 0.029   61.0 350 2440  324,000 2.3 132.8 11 54 A 0.129 103  805^(d) 85,000 9.8 124.1 24 55 A 0.129 153  402 1187^(d ) 190,000 11.7127.0 15 56 A 0.033  78^(f) 1178 2356^(d ) 347,000 3.0 136.1  5 57 SHOP0.129  4 15.5  44 2,000 1.4 broad ˜112 17 58 SHOP 0.129   11.1  86^(d,e) 2,600 1.5 120.7  12^(g) ^(a)Polymerization reactions werecarried out in a steel bomb with 1000 mL benzene and 100 mL Et₂O at 500psig of ethylene without temperature control. ^(b)SHOP is a commerciallyavailable catalyst (see U.S. Pat. No. 4,716,205 for details ofcatalyst). ^(c)TON is turn over number which is measure of catalystactivity as a rate per hour. ^(d)No ether additive used in thepolymerization reaction. ^(e)Reaction run with temperature control.^(f)Ethylene pressure was 350 psig. ^(g)Some olefinic species detected.

Table 9 reveals that catalyst activity is generally enhanced at higherethylene pressure. The Table also compares the activity of a subjectcatalyst with the SHOP catalyst. The activity of the subject catalyst issignificantly higher (as much as 10 times greater) and the polymerproduced has lower branching and higher molecular weight than observedwith polymerizations using the SHOP catalyst, with or without Lewis baseadditive. Table 9 further indicates that polyethylene yield was highestwithout the Lewis base present.

EXAMPLE LI

The appropriate amount of Na salt of the product of Example XIII andbis(triphenylphosphine)nickel(phenyl)chloride were weighed into a 12 oz.Fisher Porter pressure bottle under an atmosphere of N₂ in a dry box.The solvent (90 mL of toluene) was then cannula transferred into thepressure bottle under a positive pressure of ethylene. The ethylenepressure was raised and maintained between 85 and 100 psig. Temperaturecontrol was accomplished by a water bath. Stirring of the reactionmixture was maintained by a magnetic stirrer and a stir bar. When theviscosity of the reaction mixture increased to the point where ethyleneconsumption slowed significantly, the pressure was released andadditional amounts of solvent were added. Subsequently, the mixture wasrepressurized with ethylene. After completion of the polymerizationreaction, methanol (1000 mL) and 1 N hydrochloric acid (50 mL) was addedto the toluene solution to precipitate the polymer. The polyethylene wascollected by filtration through a glass frit, washed with methanol (100mL) and dried in vacuum. The yield of polyethylene was 38.3 g. Catalystproductivity corresponded to 578 kg PE/mol Ni. The weight averagemolecular weight and polydispersity of the polymer was 348,000 and 2.2,respectively. The peak melting point was 136.5° C. as determined by DSC.

The results of this polymerization demonstrate that the catalyst of thepresent invention can be prepared in situ by mixing compound V and asource of nickel atom {R⁶(L)₂MY}.

What is claimed is:
 1. The compound represented by the formula:

wherein R independently represents hydrogen atom; C₁-C₁₁ alkyl; aryl; orsubstituted aryl, provided that R represents at least one hydrogen atom,and z is 1 when A is oxygen or sulfur or z is 2 when A is nitrogen, R¹represents a C₁-C₁₁ alkyl; aryl; substituted aryl wherein thesubstitution group is selected from C₁-C₄ alkyl, perfluoroalkyl, nitro,sulfonate or halo group; arylalkyl; siloxyl of the formula —OSiZ₃ whereZ is selected from phenyl or C₁-C₄ alkyl; or a hydrocarbyl terminatedoxyhydrocarbylene group of the formula —(BO)_(z)R⁷ wherein each Bindependently is selected from a C₁-C₄ alkylene or an arylene group, Orepresents oxygen, R⁷ represents a C₁-C₁₁ hydrocarbyl group and z is aninteger of 1 to 4; R² represents hydrogen atom, aryl, substituted aryl,C₁-C₁₁ alkyl, halogen atom or R¹ and R², together, provide ahydrocarbylene or substituted hydrocarbylene which forms an aromatic ornon-aromatic carbocyclic ring; R³ represents hydrogen; R⁴ representshydrogen atom, a C₁-C₁₁ alkyl; an aryl; substituted aryl group; or R³ orR⁴, together, provide a hydrocarbylene or substituted hydrocarbyleneforming a non-aromatic carbocyclic ring; R⁵ represents a C₁-C₁₁ alkyl;C₅-C₈ cycloalkyl; aryl group; a substituted aryl having one or bothortho positions of the aromatic group substituted with a C₁-C₄ alkyl,the para position (with respect to the N—R⁵ bond) substituted with ahydrogen, nitro, trifluoromethyl, halogen, methoxy, C₁-C₄ alkyl,sulfonate or fused or unfused aryl group; or a hydrocarbyl terminatedoxyhydrocarbylene group of the formula —(BO)_(z)R⁷); or R¹ and R⁵together form an oxyhydrocarbylene chain, —(BO)_(m)B—, wherein each B isindependently selected from a C₁-C₄ alkylene group or an arylene groupand m is an integer of 1-4; n represents an integer of 0 or 1; Xrepresents a hydrogen atom or an electron withdrawing group selectedfrom the group consisting essentially of NO₂, halo, sulfonate (SO₃ ⁻),sulfonyl ester (SO₂R), carboxyl (COO⁻), a perfluoroalkyl, and acarboxylic ester group; and A represents oxygen, nitrogen or sulfur. 2.The compound of claim 1 wherein R¹ is selected from aryl, substitutedaryl or C₃-C₆ alkyl group.
 3. The compound of claim 1 wherein R⁵ isselected from aryl or substituted aryl, alkyl or cycloalkyl.
 4. Thecompound of claim 2 wherein R⁵ is selected from aryl or substitutedaryl.
 5. The compound of claim 2 wherein R⁵ is selected from alkyl orcycloalkyl.
 6. The compound of claim 1 wherein X is selected from nitrogroup, perfluoroalkyl group, sulfonate group, or halo atom.
 7. Thecompound of claim 1 wherein R¹ is selected from t-butyl, anthracenyl,10-nitroanthracenyl, phenanthracenyl or terphenyl.
 8. The compound ofclaim 1 wherein R⁵ is 2,6-di(C₁-C₄ alkyl)phenyl group.
 9. The compoundof claim 7 wherein R⁵ is 2,6-di(isopropyl)phenyl.
 10. The compound ofclaim 1 wherein X is selected from nitro, sulfonate or perfluoromethyl.11. The compound of claim 1 wherein R¹ is selected from a hydrocarbylterminated oxyhydrocarbylene group represented by the formula—(BO)_(z)R⁷ wherein B is independently selected from a C₁-C₄ alkylene orarylene, O is oxygen, R⁷ is a C₁-C₁₁ hydrocarbyl and z is 1-4.
 12. Thecompound of claim 1 wherein R⁵ is selected from an aryl groupsubstituted with a hydrocarbyl terminated oxyhydrocarbylene grouprepresented by the formula —(BO)_(z)R⁷ wherein B is independentlyselected from a C₁-C₄ alkylene or an arylene, O is oxygen, R⁷ is aC₁-C₁₁ hydrocarbyl and z is 1-4.
 13. The compound of claim 1 wherein R⁵is selected from a 2,6-di(C₁-C₄ alkyl)phenyl and R¹ is phenanthracenyl.14. The compound of claim 1 wherein R⁵ is selected from a 2,6-di(C₁-C₄alkyl)phenyl and R¹ is phenyl.
 15. The compound of claim 1 wherein R¹and R⁵ together represent a polyoxyhydrocarbylene group.
 16. Thecompound of claim 12 wherein R⁵ is a 2,6-di(C₁-C₄ alkyl)-4-nitrophenylgroup.
 17. The compound of claim 15 wherein X is selected from nitrogroup.
 18. The compound of claim 1 wherein X is selected from the groupconsisting of nitro group, perfluoroalkyl group, sulfonate group andhalo atom.
 19. The compound of claim 11 wherein R¹ and R⁵ togetherrepresent an oxyalkylene group.
 20. The compound of claim 1 wherein R¹is anthracenyl; R², R³ and R⁴ are each hydrogen; R⁵ is2,6-di(isopropyl)phenyl; A is oxygen; and X is hydrogen.
 21. Thecompound of claim 1 wherein R¹ is phenanthracenyl; R², R³ and R⁴ areeach hydrogen; R⁵ is 2,6-di(isopropyl)phenyl; A is oxygen; and X ishydrogen.
 22. The compound of claim 1 wherein R¹ is phenyl; R², R³ andR⁴ are each hydrogen; R⁵ is 2,6-di(isopropyl)phenyl; A is oxygen; and Xis hydrogen.
 23. The compound of claim 1 wherein R¹ is anthracenyl; R²,R³ and R⁴ are each hydrogen; R⁵ is 2,6-di(isopropyl)-4-nitrophenyl; A isoxygen; and X is hydrogen.
 24. The compound of claim 1 wherein R¹ is10-nitroanthracenyl; R², R³ and R⁴ are each hydrogen; R⁵ is2,6-di(isopropyl)phenyl; A is oxygen; and X is nitro.
 25. The compoundof claim 1 wherein R¹ is phenyl; R², R³ and R⁴ are each hydrogen; R⁵ is2,6-di(isopropyl)phenyl; A is oxygen; and X is nitro.
 26. The compoundof claim 1 wherein R¹ is 10-nitroanthracenyl; R², R³ and R⁴ are eachhydrogen; R⁵ is 2,6-di(isopropyl)-4-nitrophenyl; A is oxygen; and X isnitro.
 27. The compound of claim 1 wherein R¹ is phenanthracenyl; R², R³and R⁴ are each hydrogen; R⁵ is 2,6-di(isopropyl)phenyl; A is oxygen;and X is nitro.
 28. The compound of claim 1 wherein R¹ is10-nitroanthracenyl; R², R³ and R⁴ are each hydrogen; R⁵ is2,6-di(isopropyl)phenyl; A is oxygen; and X is hydrogen.
 29. Thecompound of claim 1 wherein R¹ is terphenyl; R², R³ and R⁴ are eachhydrogen; R⁵ is 2,6-di(isopropyl)phenyl; A is oxygen; and X is hydrogen.30. The compound of claim 1 wherein R¹ is terphenyl; R², R³ and R⁴ areeach hydrogen; R⁵ is 2,6-di(isopropyl)-4-nitrophenyl; A is oxygen; and Xis hydrogen.
 31. The compound of claim 1 wherein R¹ is terphenyl; R², R³and R⁴ are each hydrogen; R⁵ is 2,6-di(isopropyl)phenyl; A is oxygen;and X is nitro.
 32. The compound of claim 1 wherein R¹ is terphenyl; R²,R³ and R⁴ are each hydrogen; R⁵ is 2,6-di(isopropyl)-4-nitrophenyl; A isoxygen; and X is nitro.
 33. The compound of claim 1 wherein R¹ is10-nitroanthracenyl; R², R³ and R⁴ are each hydrogen; R⁵ is2,6-di(isopropyl)phenyl; A is oxygen; and X is nitro.
 34. The compoundof claim 1 wherein R¹ is phenyl; R², R³ and R⁴ are each hydrogen; R⁵ is2,6-di(isopropyl)-4-nitrophenyl; A is oxygen; and X is hydrogen.
 35. Thecompound of claim 1 wherein R¹ is phenyl; R², R³ and R⁴ are eachhydrogen; R⁵ is 2,6-di(isopropyl)-4-nitrophenyl; A is oxygen; and X isnitro.
 36. The compound of claim 13 wherein R⁵ is a 2,6-di(C₁-C₄alkyl)-4-nitrophenyl group.
 37. The compound of claim 14 wherein R⁵ is a2,6-di(C₁-C₄ alkyl)-4-nitrophenyl group.
 38. The compound of claim 1wherein X is selected from nitro group.
 39. The compound of claim 1wherein R¹ is a hydrocarbyl terminated oxyhydrocarbylene group,—(BO)_(z)R⁷; R², R³, R⁴ and X are each hydrogen; R⁵ is selected fromhydrogen or a 2,6-di(C₁-C₄ alkyl)phenyl; and A is nitrogen.